Composite film for superstrate solar cell having conductive film and electroconductive reflective film formed by applying composition containing metal nanoparticles and comprising air pores of preset diameter in contact surface

ABSTRACT

A composite film for a superstrate solar cell or a substrate solar cell has a transparent conductive film and a conductive reflective film, wherein the transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition or dispersion containing microparticles of a conductive oxide, the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles, the average diameter of holes occurring at the contact surface of the conductive reflective film on either the side of the photovoltaic layer or the side of the transparent conductive film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm 2 .

TECHNICAL FIELD

The present invention relates to a composite film having two layers, namely a transparent conductive film and a conductive reflective film, and also to a method for producing such a composite film. More specifically, the present invention relates to a composite film that is ideal for use within a superstrate thin-film solar cell or substrate solar cell, and a method for producing such a composite film.

This application claims priority on Japanese Patent Application No. 2007-236546, filed on Sep. 12, 2007, Japanese Patent Application No. 2008-205849, filed on Aug. 8, 2008, Japanese Patent Application No. 2008-205862, filed on Aug. 8, 2008, Japanese Patent Application No. 2008-205867, filed on Aug. 8, 2008, Japanese Patent Application No. 2008-205870, filed on Aug. 8, 2008, Japanese Patent Application No. 2008-224497, filed on Sep. 2, 2008, Japanese Patent Application No. 2008-224499, filed on Sep. 2, 2008, Japanese Patent Application No. 2008-224508, filed on Sep. 2, 2008, Japanese Patent Application No. 2008-224513, filed on Sep. 2, 2008, and Japanese Patent Application No. 2008-224515, filed on Sep. 2, 2008, the contents of which are incorporated herein by reference.

BACKGROUND ART

Recently, concerns over environmental conservation have lead to considerable research and development in the field of clean energy. Amongst this research, solar cells are attracting much attention due to the limitless nature of the sunlight that acts as the power source, and the fact that solar cells are non-polluting. Conventionally, electric power generation from sunlight using solar cells has employed bulk solar cells, which are prepared by producing bulk crystals of single crystal silicon or polycrystalline, and then slicing these crystals to generate thick sheet-like semiconductors. However, large amounts of time and energy are required to grow the silicon crystals used in these bulk solar cells, and the subsequent production process also requires complex steps. As a result, improving the mass productivity is difficult, and providing low-cost solar cells has proven problematic.

On the other hand, in the case of thin-film semiconductor solar cells (hereafter referred to as “thin-film solar cells”) that use a semiconductor such as an amorphous silicon having a thickness of not more than several micrometers, a semiconductor layer of the desired thickness that acts as the photovoltaic layer need simply be formed on an inexpensive substrate of glass or stainless steel or the like. Accordingly, because these thin-film solar cells are thin and lightweight, are cheap to produce, and can be easily produced as large surface area cells, it is thought that they will be the predominant form of solar cells in the future.

Thin-film solar cells are classified as superstrate cells or substrate cells depending on their structure. In a superstrate solar cell, in which the incident light enters the cell from the side of the transparent substrate, the cell typically has a structure in which the substrate, a transparent electrode, a photovoltaic layer, and a back electrode are formed in sequence. In contrast, in a substrate solar cell, a structure is adopted in which the substrate, a back electrode, a photovoltaic layer, and a transparent electrode are formed in sequence. In a superstrate solar cell in which the photovoltaic layer is formed of a silicon-based material, investigations have been conducted into enhancing the electric power generation efficiency by adopting a structure in which a transparent electrode, an amorphous silicon, a polycrystalline silicon, and a back electrode are formed in sequence (for example, see Non-Patent Document 1). In the structure disclosed in Non-Patent Document 1, the amorphous silicon and the polycrystalline silicon constitute the photovoltaic layer.

Particularly in those cases where the photovoltaic layer is formed of a silicon-based material, because the absorption coefficient for the photovoltaic layer is comparatively small, if the photovoltaic layer is formed with a thickness in the order of several micrometers, then a portion of the incident light passes through the photovoltaic layer, and this transmitted light is unable to contribute to electric power generation. Accordingly, generally, either the back electrode is formed as a reflective film, or a reflective film is formed on top of the back electrode, thereby reflecting the light that is transmitted through the photovoltaic layer without undergoing absorption and returning the light to the photovoltaic layer for a second time, thus increasing the electric power generation efficiency.

In previous thin-film solar cell development, the electrode and the reflective film have been formed using a vacuum deposition method such as sputtering or the like. However, because maintaining and operating a large-scale vacuum deposition apparatus requires enormous cost, it is anticipated that lower cost production processes using wet film formation methods will be developed.

As an example of a conductive reflective film formed using a wet film formation method, a method has been disclosed in which a reflective film formed on the back side of the photovoltaic element is formed using an electroless plating method (for example, see Patent Document 1).

Further, a simpler method is also being investigated in which a metal having a high reflectance such as silver is converted to nanoparticles, and these nanoparticles are then applied by a coating method (for example, see Patent Document 2). Furthermore, a method that involves the application of metal nanoparticles has also been disclosed as a method of forming a metal coating having high metallic gloss similar to a plating layer on the surface of a substrate (for example, see Patent Document 3). Moreover, in a superstrate solar cell that employs a substrate-transparent electrode-photovoltaic layer-transparent electrode-back reflective electrode type structure, one example of a method of forming the transparent electrode positioned adjacent to the substrate includes applying a coating liquid containing microparticles of a conductive oxide dispersed within a dispersion medium, and then using a heating method to dry and cure the coating liquid (for example, see Patent Document 4).

However, the electroless plating method disclosed in the aforementioned Patent Document 1 includes steps of forming a plating protective film on the surface, subsequently treating the surface to undergo the plating treatment with a hydrofluoric acid solution, and then dipping the structure in an electroless plating solution, meaning not only is the method complex, but the generation of considerable amounts of waste liquids can be expected.

In the methods of Patent Documents 2 and 3 that involved the application of metal nanoparticles, the reflectance when evaluated from the substrate side of the reflective film applied to the substrate surface (hereafter referred to as “the back side reflectance”) tends to be inferior to the reflectance on the exposed surface on the opposite side (hereafter referred to as “the surface reflectance”). It is thought that this difference is because holes are formed between the reflective film and the substrate, and light undergoes repeated reflection within these holes, resulting in a reduction in the reflectance. Further, in those cases where reflected light that has passed through a hole is irradiated onto the substrate at an incident angle that is larger than the critical angle, the reflected light undergoes total reflection at the interface between the hole and the substrate, and it is thought that the reflectance decreases as a result of an increase in this type of total reflection. Furthermore, in the metal nanoparticle coating methods disclosed in Patent Documents 2 and 3, only the conductive reflective film is formed by a coating method, and neither method represents a process in which both the conductive reflective film and the transparent conductive film are formed by a coating method.

In the aforementioned Patent Document 4, the wet deposition method is used only for the transparent conductive film positioned adjacent to the substrate in the superstrate solar cell, and the transparent conductive film positioned adjacent to the back reflective, electrode is formed by a sputtering method that represents a conventionally employed vacuum process.

Non-Patent Document 1: Shozo Yanagida et al., “The leading edge of thin-film solar cell development—towards higher efficiency, mass productivity, and more widespread use”, NTS Co., Ltd., March 2005, page 113, FIG. 1(a)

Patent Document 1: Japanese Unexamined Patent Application, First Publication No. Hei 05-95127 (claim 1, paragraph [0015])

Patent Document 2: Japanese Unexamined Patent Application, First Publication No. Hei 09-246577 (paragraph [0035])

Patent Document 3: Japanese Unexamined Patent Application, First Publication No. 2000-239853 (claim 3, paragraph [0009])

Patent Document 4: Japanese Unexamined Patent Application, First Publication No. Hei 10-12059 (paragraphs [0028] and [0029])

DISCLOSURE OF INVENTION Problems to be Solved by the Invention

A first object of the present invention is to provide a composite film for a superstrate solar cell having a transparent conductive film and a conductive reflective film formed using a wet coating method without causing a deterioration in the back side reflectance.

A second object of the present invention is to provide a composite film for a substrate solar cell having a transparent conductive film and a conductive reflective film formed using a wet coating method, which has a high degree of reflectance.

A third object of the present invention is to provide a process that enables a composite film for a superstrate solar cell or a composite film for a substrate solar cell to be produced comparatively cheaply, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method.

Means to Solve the Problems

A composite film for a superstrate thin-film solar cell according to a first aspect of the present invention has two layers composed of a transparent conductive film formed on a photovoltaic layer of the superstrate thin-film solar cell and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition containing microparticles of a conductive oxide, the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles, the average diameter of holes occurring at the substrate-side contact surface of the conductive reflective film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm².

For the composite film for a superstrate thin-film solar cell according to the first aspect of the present invention, the transparent conductive film composition may include either one or both of a polymeric binder and a non-polymeric binder that cure upon heating.

The polymeric binder incorporated within the transparent conductive film composition may be one or more binders selected from the group consisting of acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers.

The polymeric binder incorporated within the transparent conductive film composition may include one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.

The non-polymeric binder incorporated within the transparent conductive film composition may be one or more binders selected from the group consisting of metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates.

The metal contained within the metal soap, metal complex or metal alkoxide that functions as the non-polymeric binder may be aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony.

The transparent conductive film composition may include one or more coupling agents selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents.

The conductive reflective film may include one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The proportion of silver among the metal elements contained within the conductive reflective film may be 75% by mass or more.

The thickness of the conductive reflective film may be within a range from 0.05 to 2.0 μm.

Of the metal nanoparticles incorporated within the conductive reflective film, particles having a particle size within a range from 10 to 50 nm may represent a number average of not less than 70%.

The conductive reflective film composition may contain 75% by mass or more of silver nanoparticles as the metal nanoparticles, the metal nanoparticles may be chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms, and the metal nanoparticles may include a number average of not less than 70% of metal nanoparticles for which the primary particle size is within a range from 10 to 100 nm.

The conductive reflective film composition may include at least 0.02% by mass but less than 25% by mass of metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.

The conductive reflective film composition may contain not less than 1% by mass of water and not less than 2% by mass of an alcohol as a dispersion medium.

The conductive reflective film composition may include one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils.

The organic polymer contained within the conductive reflective film composition may be one or more polymers selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The metal oxide contained within the conductive reflective film composition may be an oxide or composite oxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The metal hydroxide contained within the conductive reflective film composition may be a hydroxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The organometallic compound contained within the conductive reflective film composition may be a metal soap, metal complex or metal alkoxide of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.

A method for producing a composite film for a superstrate thin-film solar cell according to the first aspect of the present invention includes forming a transparent conductive coating by using a wet coating method to apply a transparent conductive film composition to a photovoltaic layer of the superstrate thin-film solar cell that has been laminated on a substrate with a first transparent conductive film disposed therebetween, forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition to the transparent conductive coating, and subsequently baking the substrate having the transparent conductive coating and the conductive reflective coating formed thereon at a temperature within a range from 130 to 400° C., thereby forming two layers composed of a second transparent conductive film having a thickness of 0.03 to 0.5 μm and a conductive reflective film having a thickness of 0.05 to 2.0 μm.

In the method for producing a composite film for a superstrate thin-film solar cell according to the first aspect of the present invention, the wet coating method may be a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method.

A composite film for a superstrate solar cell according to a second aspect of the present invention has a transparent conductive film formed on a photovoltaic layer of a superstrate thin-film solar cell, and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the photovoltaic layer, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, the transparent conductive film has a thickness of 0.01 to 0.5 μm in a state where the entire surface of the conductive oxide microparticles layer is covered with the binder layer, the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the transparent conductive film and subsequently performing baking, the conductive reflective film has a thickness of 0.05 to 2.0 μm, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the photovoltaic layer is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm².

For the composite film for a superstrate solar cell according to the second aspect of the present invention, the binder dispersion may include either one or both of a polymeric binder and a non-polymeric binder that cure upon heating.

The polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers.

The polymeric binder incorporated within the binder dispersion may include one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.

The non-polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of alkoxysilanes, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates.

The dispersion of the conductive oxide microparticles may include one or more coupling agents selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents.

The conductive reflective film may include one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The proportion of silver among the metal elements contained within the conductive reflective film may be 75% by mass or more.

The thickness of the conductive reflective film may be within a range from 0.05 to 2.0 μm.

Of the metal nanoparticles incorporated within the conductive reflective film, particles having a particle size within a range from 10 to 50 nm may represent a number average of not less than 70%.

The conductive reflective film may be formed using a conductive reflective film composition, wherein the conductive reflective film composition contains 75% by mass or more of silver nanoparticles as the metal nanoparticles, the metal nanoparticles may be chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms, and the metal nanoparticles include a number average of not less than 70% of metal nanoparticles for which the primary particle size is within a range from 10 to 100 nm.

The conductive reflective film may be formed using a conductive reflective film composition that contains at least 0.02% by mass but less than 25% by mass of metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.

The conductive reflective film may be formed using a conductive reflective film composition that contains not less than 1% by mass of water and not less than 2% by mass of an alcohol as a dispersion medium.

The conductive reflective film may be formed using a conductive reflective film composition that contains one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils.

The organic polymer contained within the conductive reflective film composition may be one or more polymers selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The metal oxide contained within the conductive reflective film composition may be an oxide or composite oxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The metal hydroxide contained within the conductive reflective film composition may be a hydroxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The organometallic compound contained within the conductive reflective film composition may be a metal soap, metal complex or metal alkoxide of at least one metal selected from the group consisting of silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.

A method for producing a composite film for a superstrate solar cell according to the second aspect of the present invention includes forming a transparent conductive coating by using a wet coating method to apply a dispersion of conductive oxide microparticles and a binder dispersion to a photovoltaic layer of the superstrate solar cell that has been laminated on a substrate with a first transparent conductive film disposed therebetween, forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition to the transparent conductive coating, and subsequently baking the substrate having the transparent conductive coating and the conductive reflective coating formed thereon at a temperature within a range from 130 to 400° C., thereby forming a composite film having a second transparent conductive film having a thickness of 0.01 to 0.5 μm and a conductive reflective film having a thickness of 0.05 to 2.0 μm, wherein the transparent conductive coating is formed by forming a coating of the conductive oxide microparticles by applying the dispersion of the conductive oxide microparticles, and subsequently impregnating the coating of the conductive oxide microparticles with the binder dispersion using a wet coating method, and the second transparent conductive film has a conductive oxide microparticles layer obtained by baking the coating of the conductive oxide microparticles, and a binder layer obtained by baking the coating of the binder dispersion that covers the entire surface of the conductive oxide microparticles layer.

In the method for producing a composite film for a superstrate solar cell according to the second aspect of the present invention, the wet coating method may be a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method.

A composite film for a substrate solar cell according to a third aspect of the present invention has two layers composed of a conductive reflective film formed on a substrate and a transparent conductive film formed on top of the transparent conductive film, wherein the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles, the transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition containing microparticles of a conductive oxide, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the transparent conductive film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm².

For the composite film for a substrate solar cell according to the third aspect of the present invention, the transparent conductive film composition may include either one or both of a polymeric binder and a non-polymeric binder that cure upon heating.

The polymeric binder incorporated within the transparent conductive film composition may be one or more binders selected from the group consisting of acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers.

The polymeric binder incorporated within the transparent conductive film composition may include one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.

The non-polymeric binder incorporated within the transparent conductive film composition may be one or more binders selected from the group consisting of metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates.

The metal contained within the metal soap, metal complex or metal alkoxide that functions as the non-polymeric binder may be aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony.

The transparent conductive film composition may include one or more coupling agents selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents.

The conductive reflective film may include one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The proportion of silver among the metal elements contained within the conductive reflective film may be 75% by mass or more.

The thickness of the conductive reflective film may be within a range from 0.05 to 2.0 μm.

Of the metal nanoparticles incorporated within the conductive reflective film, particles having a particle size within a range from 10 to 50 nm may represent a number average of not less than 70%.

The conductive reflective film composition may contain 75% by mass or more of silver nanoparticles as the metal nanoparticles, the metal nanoparticles may be chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms, and the metal nanoparticles may include a number average of not less than 70% of metal nanoparticles for which the primary particle size is within a range from 10 to 100 nm.

The conductive reflective film composition may include at least 0.02% by mass but less than 25% by mass of metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.

The conductive reflective film composition may contain not less than 1% by mass of water and not less than 2% by mass of an alcohol as a dispersion medium.

The conductive reflective film composition may include one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils.

The organic polymer contained within the conductive reflective film composition may be one or more polymers selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The metal oxide contained within the conductive reflective film composition may be an oxide or composite oxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The metal hydroxide contained within the conductive reflective film composition may be a hydroxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The organometallic compound contained within the conductive reflective film composition may be a metal soap, metal complex or metal alkoxide of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.

A method for producing a composite film for a substrate solar cell according to the third aspect of the present invention includes forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition to a substrate, subsequently baking the substrate having the conductive reflective coating formed thereon at a temperature of 130 to 400° C. to form a conductive reflective film, forming a transparent conductive coating by using a wet coating method to apply a transparent conductive film composition to the conductive reflective film, and subsequently baking the substrate having the conductive reflective coating formed thereon at a temperature within a range from 130 to 400° C. to form a transparent conductive film, thereby forming two layers composed of a conductive reflective film having a thickness of 0.05 to 2.0 μm and a transparent conductive film having a thickness of 0.01 to 0.5 μm.

In the method for producing a composite film for a substrate solar cell according to the third aspect of the present invention, the wet coating method may be a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method.

A composite film for a substrate solar cell according to a fourth aspect of the present invention has a conductive reflective film formed on a substrate, and a transparent conductive film formed on top of the conductive reflective film, wherein the conductive reflective film is formed by forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the substrate and subsequently baking the conductive reflective coating, the conductive reflective film has a thickness of 0.05 to 2.0 μm, the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the conductive reflective coating, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, the transparent conductive film has a thickness of 0.01 to 0.5 μm in a state where the entire surface of the conductive oxide microparticles layer is covered with the binder layer, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the transparent conductive film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm².

For the composite film for a substrate solar cell according to the fourth aspect of the present invention, the binder dispersion may include either one or both of a polymeric binder and a non-polymeric binder that cure upon heating.

The polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers.

The polymeric binder incorporated within the binder dispersion may include one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.

The non-polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of alkoxysilanes, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates.

The dispersion of the conductive oxide microparticles may include one or more coupling agents selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents.

The conductive reflective film may include one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The proportion of silver among the metal elements contained within the conductive reflective film may be 75% by mass or more.

The thickness of the conductive reflective film may be within a range from 0.05 to 2.0 μm.

Of the metal nanoparticles incorporated within the conductive reflective film, particles having a particle size within a range from 10 to 50 nm may represent a number average of not less than 70%.

The conductive reflective film may be formed using a conductive reflective film composition, wherein the conductive reflective film composition contains 75% by mass or more of silver nanoparticles as the metal nanoparticles, the metal nanoparticles may be chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms, and the metal nanoparticles include a number average of not less than 70% of metal nanoparticles for which the primary particle size is within a range from 10 to 100 nm.

The conductive reflective film may be formed using a conductive reflective film composition that contains at least 0.02% by mass but less than 25% by mass of metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.

The conductive reflective film may be formed using a conductive reflective film composition that contains not less than 1% by mass of water and not less than 2% by mass of an alcohol as a dispersion medium.

The conductive reflective film may be formed using a conductive reflective film composition that contains one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils.

The organic polymer contained within the conductive reflective film composition may be one or more polymers selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The metal oxide contained within the conductive reflective film composition may be an oxide or composite oxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The metal hydroxide contained within the conductive reflective film composition may be a hydroxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The organometallic compound contained within the conductive reflective film composition may be a metal soap, metal complex or metal alkoxide of at least one metal selected from the group consisting of silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.

A method for producing a composite film for a substrate solar cell according to the fourth aspect of the present invention includes forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition to a substrate, subsequently forming a conductive reflective film by baking the substrate having the conductive reflective coating formed thereon at a temperature within a range from 130 to 400° C., forming a transparent conductive coating by using a wet coating method to apply a dispersion of conductive oxide microparticles and a binder dispersion to the conductive reflective coating, and subsequently forming a transparent conductive film by baking the substrate having the transparent conductive coating formed thereon at a temperature within a range from 130 to 400° C., thereby producing a composite film having a transparent conductive film having a thickness of 0.01 to 0.5 μm and a conductive reflective film having a thickness of 0.05 to 2.0 μm, wherein the transparent conductive coating is formed by forming a coating of the conductive oxide microparticles by applying the dispersion of the conductive oxide microparticles, and subsequently impregnating the coating of the conductive oxide microparticles with the binder dispersion using a wet coating method, and the transparent conductive film has a conductive oxide microparticles layer obtained by baking the coating of the conductive oxide microparticles, and a binder layer obtained by baking the coating of the binder dispersion that covers the entire surface of the conductive oxide microparticles layer.

In the method for producing a composite film for a substrate solar cell according to the fourth aspect of the present invention, the wet coating method may be a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method.

A composite film for a superstrate solar cell according to a fifth aspect of the present invention has a transparent conductive film formed on a photovoltaic layer of the superstrate solar cell, and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the photovoltaic layer, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method and subsequently performing baking, the transparent conductive film has a first layer containing a binder component on top of the photovoltaic layer and a second layer containing no binder component in which 1 to 30% of the volume of the first layer protrudes from the first layer, the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the transparent conductive film and subsequently performing baking, the conductive reflective film has a thickness of 0.05 to 2.0 μm, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the photovoltaic layer is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm².

For the composite film for a superstrate solar cell according to the fifth aspect of the present invention, the binder dispersion may include either one or both of a polymeric binder and a non-polymeric binder that cure upon heating.

The polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers.

The polymeric binder incorporated within the binder dispersion may include one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin.

The non-polymeric binder incorporated within the binder dispersion may be one or more binders selected from the group consisting of alkoxysilanes, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates.

The dispersion of the conductive oxide microparticles may include one or more coupling agents selected from the group consisting of silane coupling agents, aluminum coupling agents and titanium coupling agents.

The conductive reflective film may include one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The proportion of silver among the metal elements contained within the conductive reflective film may be 75% by mass or more.

The thickness of the conductive reflective film may be within a range from 0.05 to 2.0

Of the metal nanoparticles incorporated within the conductive reflective film, particles having a particle size within a range from 10 to 50 nm may represent a number average of not less than 70%.

The conductive reflective film may be formed using a conductive reflective film composition, wherein the conductive reflective film composition contains 75% by mass or more of silver nanoparticles as the metal nanoparticles, the metal nanoparticles may be chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms, and the metal nanoparticles include a number average of not less than 70% of metal nanoparticles for which the primary particle size is within a range from 10 to 100 nm.

The conductive reflective film may be formed using a conductive reflective film composition that contains at least 0.02% by mass but less than 25% by mass of metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese.

The conductive reflective film may be formed using a conductive reflective film composition that contains not less than 1% by mass of water and not less than 2% by mass of an alcohol as a dispersion medium.

The conductive reflective film may be formed using a conductive reflective film composition that contains one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils.

The organic polymer contained within the conductive reflective film composition may be one or more polymers selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses.

The metal oxide contained within the conductive reflective film composition may be an oxide or composite oxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The metal hydroxide contained within the conductive reflective film composition may be a hydroxide containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

The organometallic compound contained within the conductive reflective film composition may be a metal soap, metal complex or metal alkoxide of at least one metal selected from the group consisting of silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin.

A method for producing a composite film for a superstrate solar cell according to the fifth aspect of the present invention includes forming a transparent conductive coating by using a wet coating method to apply a dispersion of conductive oxide microparticles and a binder dispersion to a photovoltaic layer of the superstrate solar cell that has been laminated on a substrate with a first transparent conductive film disposed therebetween, forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition to the transparent conductive coating, and subsequently baking the substrate having the transparent conductive coating and the conductive reflective coating formed thereon at a temperature within a range from 130 to 400° C., thereby forming a composite film having a second transparent conductive film having a thickness of 0.01 to 0.5 μm and a conductive reflective film having a thickness of 0.05 to 2.0 μm, wherein the transparent conductive coating is formed by forming a coating of the conductive oxide microparticles by applying the dispersion of the conductive oxide microparticles, and subsequently impregnating the coating of the conductive oxide microparticles with the binder dispersion using a wet coating method, and the second transparent conductive film has a first layer containing a binder component on top of the photovoltaic layer and a second layer containing no binder component in which 1 to 30% of the volume of the first layer protrudes from the first layer.

In the method for producing a composite film for a superstrate solar cell according to the fifth aspect of the present invention, the wet coating method may be a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method.

Effect of the Invention

The composite film for a superstrate thin-film solar cell according to the first aspect of the present invention has two layers composed of a transparent conductive film formed on a photovoltaic layer of the superstrate thin-film solar cell, and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition containing conductive oxide microparticles, and the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles. As a result, the transparent conductive film is formed with a lower refractive index than that of a transparent conductive film formed using a vacuum deposition method such as sputtering, meaning an increased reflection effect is achieved at the conductive reflective film, and a satisfactory reflectance can be obtained. Furthermore, the average diameter of holes occurring at the substrate-side contact surface of the conductive reflective film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². As a result, when a transparent substrate having a transmittance of at least 98% is used, a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm.

Furthermore, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method, the composite film can be produced comparatively cheaply.

The composite film for a superstrate solar cell according to the second aspect of the present invention has a transparent conductive film formed on a photovoltaic layer of a superstrate thin-film solar cell, and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the photovoltaic layer, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, and the transparent conductive film has a thickness of 0.01 to 0.5 μm in a state where the entire surface of the conductive oxide microparticles layer is covered with the binder layer. As a result, an increased reflection effect is achieved at the conductive reflective film, and a satisfactory reflectance can be obtained. Furthermore, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the photovoltaic layer is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². As a result, when a transparent substrate having a transmittance of at least 98% is used, a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm.

Furthermore, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method, the composite film can be produced comparatively cheaply.

The composite film for a substrate solar cell according to the third aspect of the present invention has two layers composed of a conductive reflective film formed on a substrate and a transparent conductive film formed on top of the conductive reflective film, wherein the conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles, and the transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition containing microparticles of a conductive oxide. As a result, the transparent conductive film is formed with a lower refractive index than that of a transparent conductive film formed using a vacuum deposition method such as sputtering, meaning an increased reflection effect is achieved at the conductive reflective film, and a satisfactory reflectance can be obtained. Furthermore, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the transparent conductive film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². As a result, a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm.

Furthermore, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method, the composite film can be produced comparatively cheaply.

The composite film for a substrate solar cell according to the fourth aspect of the present invention has a conductive reflective film formed on a substrate, and a transparent conductive film formed on top of the conductive reflective film, wherein the conductive reflective film is formed by forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the substrate and subsequently baking the conductive reflective coating, the conductive reflective film has a thickness of 0.05 to 2.0 μm, the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the conductive reflective coating, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, and the transparent conductive film has a thickness of 0.01 to 0.5 μm in a state where the entire surface of the conductive oxide microparticles layer is covered with the binder layer. As a result, an increased reflection effect is achieved at the conductive reflective film, and a satisfactory reflectance can be obtained. Furthermore, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the transparent conductive film is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². As a result, when a transparent substrate having a transmittance of at least 98% is used, a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm.

Furthermore, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method, the composite film can be produced comparatively cheaply.

The composite film for a superstrate solar cell according to the fifth aspect of the present invention has a transparent conductive film formed on a photovoltaic layer of the superstrate solar cell, and a conductive reflective film formed on top of the transparent conductive film, wherein the transparent conductive film is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the photovoltaic layer, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method and subsequently performing baking, and the transparent conductive film has a first layer containing a binder component on top of the photovoltaic layer and a second layer containing no binder component in which 1 to 30% of the volume of the first layer protrudes from the first layer. As a result, an increased reflection effect is achieved at the conductive reflective film, and a satisfactory reflectance can be obtained. Furthermore, the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the photovoltaic layer is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². As a result, when a transparent substrate having a transmittance of at least 98% is used, a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm.

Furthermore, by eliminating vacuum processes such as vacuum deposition and sputtering as far as possible, and using a wet coating method, the composite film can be produced comparatively cheaply.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram that schematically illustrates a cross-section of a composite film for a superstrate thin-film solar cell according to a first embodiment of the present invention.

FIG. 2 is a diagram that schematically illustrates a cross-section of a composite film for a superstrate solar cell according to a second embodiment of the present invention.

FIG. 3 is a diagram that schematically illustrates a cross-section of the composite film for a superstrate solar cell of the second embodiment of the present invention prior to baking.

FIG. 4 is a diagram that schematically illustrates a cross-section of a composite film for a substrate solar cell according to a third embodiment of the present invention.

FIG. 5 is a diagram that schematically illustrates a cross-section of a composite film for a substrate solar cell according to a fourth embodiment of the present invention.

FIG. 6 is a diagram that schematically illustrates a cross-section of a transparent conductive coating formed during production of the composite film for a substrate solar cell according to the fourth embodiment of the present invention.

FIG. 7 is a diagram that schematically illustrates a cross-section of a composite film for a superstrate solar cell according to a fifth embodiment of the present invention.

FIG. 8 is a diagram that schematically illustrates a cross-section of the composite film for a superstrate solar cell of the fifth embodiment of the present invention prior to baking.

FIG. 9 is a diagram that schematically illustrates a cross-section of a thin-film solar cell formed in examples E1 to E37 and comparative examples E1 and E2.

FIG. 10 is a diagram that schematically illustrates a top view of a thin-film solar cell formed in examples E1 to E37 and comparative examples E1 and E2.

DESCRIPTION OF THE REFERENCE SYMBOLS

-   111 Composite film -   111 a Conductive reflective film -   111 b Second transparent conductive film -   112 Photovoltaic layer -   114 Substrate -   213 Photovoltaic layer -   214 Second transparent conductive film -   214 a Conductive oxide microparticles layer -   214 b Binder layer -   215 Conductive reflective film -   311 Substrate -   312 Composite film -   312 a Conductive reflective film -   312 b Second transparent conductive film -   313 Photovoltaic layer -   314 First transparent conductive film -   411 Substrate -   412 Conductive reflective film -   413 Second transparent conductive film -   413 a Conductive oxide microparticles layer -   413 b Binder layer -   513 Photovoltaic layer -   514 Second transparent conductive film -   514 a First layer (first particle layer) of conductive oxide     microparticles layer -   514 b Second layer (second particle layer) of conductive oxide     microparticles layer -   515 Conductive reflective film

BEST MODE FOR CARRYING OUT THE INVENTION

The best embodiments for carrying out the present invention are described below with reference to the drawings.

First Embodiment

As illustrated in FIG. 1, a superstrate thin-film solar cell typically has a structure in which a first transparent conductive film (the light incident side transparent conductive film) 113 and a photovoltaic layer 112 are laminated sequentially on top of a substrate 114, a second transparent conductive film 111 b is formed on top of the photovoltaic layer 112, and a conductive reflective film 111 a is then formed on top of the second transparent conductive film 111 b.

The first embodiment of the present invention relates to a composite film 111 for a superstrate thin-film solar cell that is composed of two layers, namely, the second transparent conductive film 111 b formed on top of the photovoltaic layer 112, and the conductive reflective film 111 a formed on top of the second transparent conductive film 111 b.

In the composite film 111 according to the first embodiment of the present invention, the second transparent conductive film 111 b is formed by using a wet coating method to apply a transparent conductive film composition containing conductive oxide microparticles. If the second transparent conductive film 111 b is formed using a vacuum deposition method such as a sputtering method, then the refractive index of the second transparent conductive film is determined by the material used as the target material, and consequently achieving the desired refractive index is problematic for a second transparent conductive film formed using a vacuum deposition method such as sputtering. In contrast, in the case of the second transparent conductive film 111 b formed using a wet coating method, because the film is formed by applying a transparent conductive film composition that is a mixture of conductive oxide microparticles and one or more other components, a film formed using such a wet coating method is capable of realizing the desired low refractive index. The refractive index of this second transparent conductive film 111 b is typically within a range from 1.5 to 2. A second transparent conductive film 111 b having a low refractive index imparts an increased reflection effect to the adjoining conductive reflective film 111 a in terms of optical design, and therefore a reflectance can be obtained that is higher than that obtainable for a conductive reflective film adjoining a second transparent conductive film having a high refractive index formed using a conventional vacuum deposition method such as sputtering.

Further, in the composite film 111 of the first embodiment of the present invention, the conductive reflective film 111 a is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the second transparent conductive film 111 b formed using the wet coating method described above. Accordingly, the formed conductive reflective film 111 a exhibits favorable film formability and has a high diffuse reflectance. When a film is formed on a substrate of glass or the like, favorable film formability and a high diffuse reflectance can be achieved even when film formation is conducted using a vacuum deposition method such as a sputtering method, but if a vacuum deposition method such as sputtering is used to form a film on top of the second transparent conductive film 111 b that has been formed using a wet coating method, then the residual solvent within the second transparent conductive film 111 b tends to exert adverse effects on the formed conductive reflective film, meaning forming a conductive reflective film with a high reflectance is difficult.

In this manner, the composite film 111 according to the first embodiment of the present invention has an improved reflection effect, in terms of optical design, imparted by the second transparent conductive film 111 b that has a low refractive index, and a higher reflectance as a result of the favorable film formability and high diffuse reflectance provided by the conductive reflective film 111 a.

Moreover, by ensuring that the average diameter of holes occurring at the contact surface of the conductive reflective film 111 a on the side of the substrate 114 is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm², a conductive reflective film 111 a is obtained for which a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm when a transparent substrate having a transmittance of at least 98% is used. This wavelength range from 500 to 1,200 nm encompasses substantially all convertible wavelengths in those cases where a polycrystalline silicon is used for the photovoltaic layer. The reason for specifying an average diameter for the holes of not more than 100 nm is that, generally, a reflectance spectrum exhibits high reflectance at the long wavelength side of the spectrum and lower reflectance at the short wavelength side, and if the average diameter of the holes exceeds 100 nm, then the inflexion point at which the reflectance starts to decrease tends to shift to a longer wavelength, meaning a favorable reflectance may become unobtainable. Furthermore, the reason for specifying an average depth for the holes of not more than 100 nm is that if the average depth of the holes exceeds 100 nm, then the gradient (slope) of the reflectance spectrum tends to increase, meaning a favorable reflectance may be unobtainable. The reason for specifying a number density for the holes of not more than 30 holes/μm² is that if the number density of the holes exceeds 30 holes/μm², then the reflectance at the long wavelength side of the spectrum tends to decrease, meaning a favorable reflectance may be unobtainable.

The average diameter of the holes is preferably within a range from 5 to 100 nm, the average depth at which the holes are positioned is preferably within a range from 5 to 100 nm, and the number density of the holes is preferably within a range from 2 to 30 holes/μm². If the values for the average diameter of the holes, the average depth at which the holes are positioned, and the number density of the holes are less than the lower limits of the above ranges, then during sintering, the elimination of gas generated by decomposition of the organic molecules of the protective agent used to chemically modify the silver nanoparticles tends to be inadequate, and as a result, there is a possibility that the remaining organic molecule residues may cause reductions in the conductivity and the reflectance of the conductive reflective film.

The conductive reflective film that constitutes part of the composite film contains one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and this facilitates the setting of the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the second transparent conductive film to not more than 100 nm, the average depth to not more than 100 nm, and the number density to not more than 30 holes/μm². Furthermore, in the conductive reflective film that constitutes part of the composite film, because the proportion of silver among the metal elements contained within the film is 75% by mass or more, a high reflectance can be achieved. If this proportion is less than 75%, then the reflectance of the conductive reflective film formed using the composition tends to decrease. Furthermore, because the thickness of the conductive reflective film that constitutes part of the composite film is within a range from 0.05 to 2.0 μm, an electrode surface resistance value of the level required of a solar cell can be obtained. Moreover, of the metal nanoparticles incorporated within the conductive reflective film that constitutes part of the composite film, because particles having a particle size within a range from 10 to 50 nm represent a number average of not less than 70%, favorable conductivity and a high reflectance are obtained.

The transparent conductive film composition used in forming the second transparent conductive film of the first embodiment of the present invention contains conductive oxide microparticles, and is a composition in which these conductive oxide microparticles are dispersed within a dispersion medium.

As the conductive oxide microparticles incorporated within the transparent conductive film composition, tin oxide powders of ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide: antimony-doped tin oxide), and zinc oxide powders containing one or more elements selected from the group consisting of Al, Co, Fe, In, Sn and Ti are preferred, and of these, ITO, ATO, AZO (Aluminum Zinc Oxide: aluminum-doped zinc oxide), IZO (Indium Zinc Oxide: indium-doped zinc oxide) and TZO (Tin Zinc Oxide: tin-doped zinc oxide) are particularly desirable. Furthermore, the proportion of the conductive oxide microparticles within the solid fraction of the transparent conductive film composition is preferably within a range from 50 to 90% by mass. The reason for specifying a conductive oxide microparticles proportion within the above range is that at proportions less than the lower limit of the range, the conductivity tends to decrease, whereas if the proportion exceeds the upper limit of the range, the adhesion tends to deteriorate undesirably. Within the above range, a proportion of 70 to 90% by mass is particularly desirable. Furthermore, in terms of ensuring favorable stability within the dispersion medium, the average particle size of the conductive oxide microparticles is preferably within a range from 10 to 100 nm, and more preferably from 20 to 60 nm.

The transparent conductive film composition is a composition that includes either one or both of a polymeric binder and a non-polymeric binder that cure upon heating. Examples of the polymeric binder include acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers. Furthermore, the polymeric binder preferably includes one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin. Examples of the non-polymeric binder include metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates. Further, the metal contained within the metal soap, metal complex or metal alkoxide is typically aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony. These polymeric binders and non-polymeric binders cure upon heating, making it possible to form a second transparent conductive film having a low haze and low volume resistivity at low temperature. The amount of these binders, reported as a proportion of the solid fraction within the transparent conductive film composition, is preferably within a range from 5 to 50% by mass, and is more preferably within a range from 10 to 30% by mass.

A coupling agent is preferably added to the transparent conductive film composition depending on the other components used. This coupling agent has the functions of improving the bonding between the conductive microparticles and the binder, and improving the adhesion between the second transparent conductive film formed from this transparent conductive film composition and the layers or conductive reflective film laminated on the substrate. Examples of the coupling agent include silane coupling agents, aluminum coupling agents and titanium coupling agents.

Examples of the silane coupling agents include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the aluminum coupling agents include the aluminum coupling agent containing acetoalkoxy groups illustrated below in formula (1). Furthermore, examples of the titanium coupling agents include the titanium coupling agents having dialkyl pyrophosphite groups illustrated below in formulas (2) to (4), and the titanium coupling agent having a dialkyl phosphite group illustrated below in formula (5).

The amount of the coupling agent, reported as a proportion of the solid fraction within the transparent conductive film composition, is preferably within a range from 0.2 to 5% by mass, and is more preferably within a range from 0.5 to 2% by mass.

Examples of the dispersion medium used in forming the transparent conductive film composition include not only water, but also alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, glycols such as ethylene glycol, and glycol ethers such as ethyl cellosolve. In order to obtain favorable film formability, the proportion of the dispersion medium within the composition is preferably within a range from 80 to 99% by mass.

Furthermore, depending on the components used, the addition of a resistance reducer or a water-soluble cellulose derivative or the like may also be preferable. The resistance reducer is preferably one or more materials selected from the group consisting of mineral acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. Specific examples include a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octylate and antimony chloride, a mixture of indium nitrate and lead acetate, and a mixture of titanium acetylacetate and cobalt octylate. The amount of these resistance reducers is preferably 0.2 to 15% by mass relative to the mass of the conductive oxide powder. A water-soluble cellulose derivative is a non-ionic surfactant, but compared with other surfactants, has an extremely powerful ability to disperse the conductive oxide powder even when added in a very small amount. Furthermore, addition of a water-soluble cellulose derivative also improves the transparency of the formed second transparent conductive film. Specific examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount added of the water-soluble cellulose derivative is preferably within a range from 0.2 to 5% by mass.

The conductive reflective film composition used in forming the conductive reflective film of the first embodiment of the present invention is a composition composed of metal nanoparticles dispersed within a dispersion medium. The metal nanoparticles typically include at least 75% by mass, and preferably 80% by mass or more of silver nanoparticles. The reason for specifying an amount of silver nanoparticles of at least 75% by mass relative to 100% by mass of all the metal nanoparticles is because at an amount less than 75% by mass, the reflectance of the conductive reflective film formed using this composition tends to decrease. Furthermore, the silver nanoparticles are chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms.

The reason for restricting the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the metal nanoparticles to a number within a range from 1 to 3 is because if the number of carbon atoms is 4 or greater, then the protective agent becomes difficult to eliminate or decompose (detach and combust) under the heat used during the baking process, meaning a large amount of organic residue tends to remain within the film, which subsequently degenerates or degrades, causing reductions in the conductivity and reflectance of the conductive reflective film.

The silver nanoparticles include a number average of not less than 70%, and preferably not less than 75%, of silver nanoparticles having a primary particle size within a range from 10 to 50 nm. The reason for ensuring that the amount of metal nanoparticles having a primary particle size within a range from 10 to 50 nm is a number average of not less than 70% relative to 100% of all the metal nanoparticles is because if this number average is less than 70%, then the specific surface area of the metal nanoparticles increases and the proportion of the particles composed of organic matter increases, meaning that even if the organic molecules are readily eliminated or decomposed (detached and combusted) under the heat used during baking, because the amount of organic molecules is large, a large amount of organic residue tends to remain within the film, and this residue may subsequently degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film, or the particle size distribution of the metal nanoparticles may broaden considerably, making the density of the conductive reflective film prone to a reduction that causes a deterioration in the conductivity and reflectance of the conductive reflective film. Moreover, another reason for specifying a primary particle size for the metal nanoparticles of 10 to 50 nm is that statistical analyses reveal that metal nanoparticles having a primary particle size within a range from 10 to 50 nm correlate with improved stability over time.

The metal nanoparticles other than the silver nanoparticles are metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, and the amount of these metal nanoparticles other than the silver nanoparticles, relative to 100% by mass of all the metal nanoparticles, is at least 0.02% by mass but less than 25% by mass, and preferably within a range from 0.03 to 20% by mass. The reason for restricting the amount of the metal nanoparticles other than silver nanoparticles to at least 0.02% by mass but less than 25% by mass relative to 100% by mass of all the metal nanoparticles is because if the amount is less than 0.02% by mass, then although no particular problems arise, amounts within the range from 0.02 to 25% by mass still produce results for the conductivity and reflectance of the conductive reflective film following a weather resistance test (a test that involves standing for 1,000 hours in a constant temperature and humidity chamber at a temperature of 100° C. and a humidity of 50%) that display no deterioration from the results prior to the weather resistance test, whereas on the other hand, if the amount is 25% by mass or greater, then the conductivity and reflectance of the conductive reflective film immediately following baking tend to decrease, and the conductivity and reflectance of the conductive reflective film following a weather resistance test tend to be inferior to the conductivity and reflectance of the conductive reflective film prior to the weather resistance test.

The conductive reflective film composition used in forming the conductive reflective film of the first embodiment of the present invention includes one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils. A metal oxide, metal hydroxide, organometallic compound or silicone oil incorporated within the composition as an additive improves the adhesion to the second transparent conductive film with no loss of conductivity, either due to chemical bonding or an anchoring effect relative to the second transparent conductive film, or due to an improvement in the wettability between the metal nanoparticles and the second transparent conductive film during the baking step.

If the conductive reflective film is formed using a composition that contains none of the above metal oxides and the like, then the surface roughness of the formed conductive reflective film increases, but in order to optimize the photovoltaic conversion efficiency, specific conditions must be satisfied for the uneven shape of the surface of the conductive reflective film, and simply increasing the surface roughness does not necessarily enable the formation of a conductive reflective film surface having superior photovoltaic conversion efficiency. By appropriate adjustment of the variety and concentration and the like of the metal oxide, as described for the first embodiment of the present invention, a surface having a surface roughness that optimizes the photovoltaic conversion efficiency can be formed.

The amount of the additives is typically within a range from 0.1 to 20%, and preferably from 0.2 to 10%, of the mass of the silver nanoparticles within the metal nanoparticles. If the amount of these additives is less than 0.1%, then there is a possibility that holes having a large average diameter may be generated, and the density of the holes may increase. An amount of the additives exceeding 20% tends to exert an adverse effect on the conductivity of the formed conductive reflective film, and may result in a volume resistivity exceeding 2×10⁻⁵ Ω·cm.

As the organic polymer used as an additive, one or more polymers selected from the group consisting of polyvinylpyrrolidone (hereafter also abbreviated as PVP), PVP copolymers and water-soluble celluloses are used. Specific examples of the PVP copolymers include PVP-methacrylate copolymers, PVP-styrene copolymers and PVP-vinyl acetate copolymers. Further, examples of the water-soluble celluloses include cellulose ethers such as hydroxypropylmethylcellulose, methylcellulose and hydroxyethylmethylcellulose.

Examples of the metal oxide used as an additive include oxides or composite oxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony. Specific examples of the composite oxides include ITO, ATO and IZO.

Examples of the metal hydroxide used as an additive include hydroxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Examples of the organometallic compound used as an additive include metal soaps, metal complexes and metal alkoxides of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin. Examples of the metal soaps include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate and molybdenum acetate. Furthermore, examples of the metal complexes include a zinc acetylacetonate complex, chromium acetylacetonate complex and nickel acetylacetonate complex. Examples of the metal alkoxides include titanium isopropoxide, methyl silicate, isocyanatopropyltrimethoxysilane and aminopropyltrimethoxysilane.

Examples of the silicone oil used as an additive include both straight silicone oils and modified silicone oils. As the modified silicone oils, oils that include organic groups introduced at a portion of the side chains of a polysiloxane (side-chain type oils), oils that include organic groups introduced at both terminals of a polysiloxane (both terminal-type oils), oils that include an organic group introduced at one of the two terminals of a polysiloxane (single terminal-type oils), and oils that include organic groups introduced at a portion of the side chains and at both terminals of a polysiloxane (side-chain, both terminal-type oils) can be used. Modified silicone oils include both reactive silicone oils and unreactive silicone oils, and a combination of both types may also be used as an additive in the first embodiment of the present invention. Reactive silicone oils include amino-modified, epoxy-modified, carboxy-modified, carbinol-modified and mercapto-modified silicone oils, as well as silicone oils modified with a number of different functional groups (such as epoxy groups, amino groups and polyether groups). Unreactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, fluorine-modified, and specific hydrophilic-modified silicone oils.

The dispersion medium used in forming the conductive reflective film composition is preferably composed of an alcohol or an alcohol-containing aqueous solution. Examples of alcohols that may be used as the dispersion medium include one or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornylhexanol and erythritol. The alcohol-containing aqueous solution preferably contains, relative to 100% by mass of the entire dispersion medium, not less than 1% by mass, and preferably 2% by mass or more of water, and not less than 2% by mass, and preferably 3% by mass or more of an alcohol. For example, in those cases where the dispersion medium is composed solely of water and an alcohol, if the medium contains 2% by mass of water, then the alcohol content is 98% by mass, whereas if the medium contains 2% by mass of the alcohol, then the water content is 98% by mass. The reason for specifying a water content of not less than 1% by mass relative to 100% by mass of the entire dispersion medium is because if the water content is less than 1% by mass, then the film obtained by using a wet coating method to apply the conductive reflective film composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate. The reason for specifying an alcohol content of not less than 2% by mass relative to 100% by mass of the entire dispersion medium is because if the alcohol content is less than 2% by mass, then in a similar manner to that described above, the film obtained by using a wet coating method to apply the composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate.

Moreover, the dispersion medium, namely the protective molecules that chemically modify the surface of the metal nanoparticles, preferably contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). If a hydroxyl group (—OH) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action. If a carbonyl group (—C═O) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then in a similar manner to that described above, the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action.

Examples of the method used for producing the conductive reflective film composition include the methods outlined below.

(a) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 3

Firstly, silver nitrate is dissolved in water such as deionized water to prepare a metal salt aqueous solution. In a separate preparation, sodium citrate is dissolved in water such as deionized water to prepare an aqueous solution of sodium citrate having a concentration of 10 to 40%, and ferrous sulfate in a particulate or powder form is then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of an inert gas such as nitrogen gas, thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions. Subsequently, with the reducing agent aqueous solution undergoing constant stirring under a stream of the above inert gas, the metal salt aqueous solution described above is added dropwise to the reducing agent aqueous solution and mixed thoroughly. During this process, it is preferable that the concentrations of the solutions are altered so that the amount added of the metal salt aqueous solution is not more than 1/10th of the amount of the reducing agent aqueous solution, as this ensures that the reaction temperature can be maintained within a range from 30 to 60° C. even if the added metal salt aqueous solution is at room temperature. Further, the mixing ratio between the two aqueous solutions is preferably adjusted so that the equivalent amount of ferrous ions added as the reducing agent is three times the equivalent amount of the metal ions, in other words, (number of mols of metal ions within the metal salt aqueous solution)×(valency of metal ions)=3×(ferrous ions within the reducing agent aqueous solution). Following completion of the dropwise addition of the metal salt aqueous solution, stirring of the resulting mixed liquid is continued for a further 10 to 300 minutes, thus forming a dispersion composed of a metal colloid. This dispersion is left to stand at room temperature, the precipitated metal nanoparticle aggregates are isolated by decantation and/or centrifugal separation and the like, water such as deionized water is added to the isolated nanoparticle aggregates to form a dispersion, a demineralization treatment is conducted using ultrafiltration, and displacement washing is then performed using an alcohol, so as to achieve a metal (silver) content within a range from 2.5 to 50% by mass. Subsequently, by separating the very coarse particles using a centrifugal separator with appropriate adjustment of the centrifugal power, silver nanoparticles are prepared in which those particles having a primary particle size within a range from 10 to 50 nm represent a number average of not less than 70%. In other words, the silver nanoparticles are prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm represents a number average of not less than 70%. By using this method, a dispersion is obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the silver nanoparticles is 3.

Subsequently, the resulting dispersion is adjusted so that the final metal content (silver content) relative to 100% by mass of the dispersion is within a range from 2.5 to 95% by mass. Further, in those cases where the dispersion medium is an alcohol-containing aqueous solution, the amounts of the water and the alcohol within the medium are preferably adjusted to amounts of not less than 1% and not less than 2% respectively. Furthermore, in those cases where further additives are included within the composition, one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils are added in the desired proportions. The amount of these additives is adjusted so as to satisfy a range from 0.1 to 20% by mass relative to 100% by mass of the obtained composition. This enables a composition to be obtained in which silver nanoparticles, which have been chemically modified with a protective agent having an organic molecular main chain in which the number of carbon atoms within the carbon skeleton is 3, are dispersed within the dispersion medium.

(b) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 2

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium malate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 2.

(c) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 1

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium glycolate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 1.

(d) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to 3

Examples of the metal that constitutes the metal nanoparticles other than silver nanoparticles include gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese. With the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with chlorauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is 3.

In those cases where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to either 1 or 2, a dispersion is prepared in the same manner as either (b) or (c) above, with the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with one of the other metal salts listed above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is either 1 or 2.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles are combined as the metal nanoparticles, then for example, if the dispersion containing silver nanoparticles produced using the above method (a) is deemed the first dispersion, and the dispersion containing metal nanoparticles other than silver nanoparticles produced using the above method (d) is deemed the second dispersion, a dispersion may be prepared by mixing at least 75% by mass of the first dispersion and less than 25% by mass of the second dispersion so that the combination of the first and second dispersions totals 100% by mass. The first dispersion is not restricted to a dispersion containing silver nanoparticles produced using the above method (a), and a dispersion containing silver nanoparticles produced using the above method (b) or a dispersion containing silver nanoparticles produced using the above method (c) may also be used.

Next is a description of a method for producing a composite film according to the first embodiment of the present invention.

In the method for producing a composite film according to the first embodiment of the present invention, first, a wet coating method is used to apply the above transparent conductive film composition to a photovoltaic layer of a superstrate solar cell that has been laminated on a substrate with a first transparent conductive film disposed therebetween. This application is conducted so that the thickness following baking is within a range from 0.03 to 0.5 μm, and preferably from 0.05 to 0.1 μm. Subsequently, the applied coating is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a transparent conductive coating. Next, a wet coating method is used to apply the above conductive reflective film composition to the transparent conductive coating. This application is conducted so that the thickness following baking is within a range from 0.05 to 2.0 μm, and preferably from 0.1 to 1.5 μm. The applied coating is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a conductive reflective coating. As the above substrate, either a transparent substrate composed of a glass, a ceramic or a polymer material, or a transparent laminate composed of two or more types of material selected from the group consisting of glass, ceramics, polymer materials and silicon can be used. Examples of polymer material substrates include substrates formed from an organic polymer such as a polyimide or PET (polyethylene terephthalate).

Moreover, the wet coating method mentioned above is preferably one of a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method, although this list is not exhaustive, and any appropriate method may be used.

Spray coating is a method in which either the dispersion is converted to a fine mist using compressed air and then applied to the substrate, or the dispersion itself is pressurized and converted to a fine mist that is then applied to the substrate. Dispenser coating is a method in which, for example, the dispersion is placed inside an injector, and the dispersion is then discharged, from a fine nozzle at the tip of the injector and applied to the substrate by depressing the injector piston. Spin coating is a method in which the dispersion is dripped onto a spinning substrate, and the dripped dispersion spreads out to the peripheral edges of the substrate under centrifugal force. Knife coating is a method in which a substrate that is separated from the tip of a knife by a predetermined gap is provided in a manner that enables the substrate to be moved horizontally, and the dispersion is supplied onto the substrate at a point upstream from the knife while the substrate is moved horizontally in the downstream direction. Slit coating is a method in which the dispersion is exuded from a narrow slit and coated onto the substrate. Inkjet coating is a method in which the dispersion is used to fill the ink cartridge of a commercially available inkjet printer, and the dispersion is then applied to the substrate by inkjet printing. Screen printing is a method in which a gauze is used as a patterning material, and the dispersion is transferred to the substrate through a print image formed on the gauze. Offset printing is a printing method that utilizes the water repellency of ink, wherein the dispersion applied to a plate is not adhered directly to the substrate, but is rather first transferred from the plate to a rubber sheet, before being subsequently transferred from the rubber sheet to the substrate. Die coating is a method in which a dispersion that has been supplied to a die is distributed using a manifold, and is then extruded in a thin film from a slit, and applied to the surface of a moving substrate. Die coating methods include slot coating, slide coating and curtain coating methods.

Finally, the substrate having the coatings formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes. The reason for conducting the application of the transparent conductive film composition so that the thickness of the second transparent conductive film following baking is within a range from 0.03 to 0.5 μm is because if the thickness following baking is less than 0.03 μm or greater than 0.5 μm, then a satisfactory improvement in the reflection cannot be obtained. Furthermore, the reason for conducting the application of the conductive reflective film composition so that the thickness of the conductive reflective film following baking is within a range from 0.05 to 2.0 μm is because if the thickness is less than 0.05 μm, then the surface resistance value becomes overly high, making it difficult to obtain the level of conductivity required of a solar cell electrode, whereas if the thickness exceeds 2.0 μm, then although there are no concerns in terms of the resulting properties, the amount of material used is more than is necessary, resulting in unnecessary material waste.

The reason for specifying a baking temperature for the substrate having the coatings formed thereon within a range from 130 to 400° C. is because at temperatures lower than 130° C., a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. In contrast, if the temperature exceeds 400° C., then any merit associated with conducting the production using a low-temperature process is lost. In other words, the production costs increase, and the productivity tends to decrease. Furthermore, amorphous silicon solar cells, microcrystalline silicon solar cells, and hybrid silicon solar cells that use both these forms of silicon are particularly susceptible to heat, and a high temperature during the baking step causes a deterioration in the conversion efficiency.

The reason for specifying a baking time within a range from 5 to 60 minutes for the substrate having the coatings formed thereon is because if the baking time is less than the lower limit of this range, then a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. Although lengthening the baking time beyond the upper limit of the above range has no adverse effects on the composite film properties, it results in an unnecessary increase in production costs and decrease in productivity. Moreover, the conversion efficiency of the solar cell also tends to deteriorate.

The composite film of the first embodiment of the present invention can be formed in the manner described above. In this manner, by using a wet coating method, the production process according to the first embodiment of the present invention is able to eliminate vacuum processes such as vacuum deposition and sputtering as far as possible, meaning the composite film can be produced comparatively cheaply.

Second Embodiment

A superstrate thin-film solar cell generally has a structure in which a first transparent conductive film (the light incident side transparent conductive film) and a photovoltaic layer are laminated sequentially on top of a substrate, a second transparent conductive film is formed on top of the photovoltaic layer, and a conductive reflective film is then formed on top of the second transparent conductive film.

The second embodiment of the present invention relates to a composite film for a superstrate solar cell having a second transparent conductive film formed on a photovoltaic layer of the superstrate solar cell, and a conductive reflective film formed on top of the second transparent conductive film.

FIG. 2 is a diagram that schematically illustrates a cross-section of the composite film according to the second embodiment of the present invention. As illustrated in FIG. 2, the special features of the structure of the composite film 216 of the second embodiment of the present invention are (1) that a second transparent conductive film 214 is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to a photovoltaic layer 213, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, and (2) that the second transparent conductive film 214 has a thickness of 0.01 to 0.5 μm in a state where the entire surface of a conductive oxide microparticles layer 214 a is covered with a binder layer 214 b.

If the second transparent conductive film is formed using a vacuum deposition method such as a sputtering method, then the refractive index of the second transparent conductive film is determined by the material used as the target material, and consequently achieving the desired refractive index is problematic for a second transparent conductive film formed using a vacuum deposition method such as sputtering. In contrast, in the case of a second transparent conductive film formed using a wet coating method, because the film is generally formed by applying a composition that is a mixture of conductive oxide microparticles and one or more other components, a film formed using such a wet coating method is capable of realizing the desired low refractive index by appropriate adjustment of the components within the composition. The refractive index of this second transparent conductive film is typically within a range from 1.5 to 2. A second transparent conductive film having a low refractive index imparts an increased reflection effect to the adjoining conductive reflective film in terms of optical design, and therefore a conductive reflective film adjoining a second transparent conductive film formed using a wet coating method exhibits a higher reflectance than that obtainable for a conductive reflective film adjoining a second transparent conductive film having a high refractive index formed using a conventional vacuum deposition method such as sputtering.

One example of a second transparent conductive film formed using a wet coating method is a simple second transparent conductive film formed by applying a composition prepared by combining conductive oxide microparticles and a binder component, and subsequently baking the applied coating. On the other hand, the second transparent conductive film in the composite film according to the second embodiment of the present invention is formed by first forming a coating of conductive oxide microparticles containing no binder component on the photovoltaic layer, subsequently applying a binder dispersion containing no conductive oxide microparticles to the layer of the conductive oxide microparticles, and then performing baking at a predetermined temperature. In other words, as illustrated in FIG. 2, the second transparent conductive film 214 of the composite film according to the second embodiment of the present invention has the binder layer 214 b that contains no conductive oxide microparticles as the upper layer. Further, the lower layer near the interface with the photovoltaic layer 213 is composed of the conductive oxide microparticles layer 214 a, which is totally covered with the binder layer 214 b, and contains a portion of the binder dispersion that impregnates the conductive oxide microparticles layer when the binder dispersion is applied. Upon baking, a portion of the particles within this conductive oxide microparticles layer 214 a undergo sintering, thereby ensuring a high degree of conductivity.

In the composite film of the second embodiment of the present invention, by forming the second transparent conductive film with the structure described above, the level of adhesion with the underlying photovoltaic layer can be improved compared with a composite film having a simple second transparent conductive film formed using a composition containing both the conductive oxide microparticles and a binder component. Furthermore, because the composite film is formed with the entire surface of the conductive oxide microparticles layer covered with the binder layer, change in the film over time is minimal.

The thickness of the second transparent conductive film 214 is within a range from 0.01 to 0.5 μm, whereas the thickness of the conductive reflective film 215 is within a range from 0.05 to 2.0 μm.

Furthermore, the conductive reflective film 215 is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the second transparent conductive film 214. Accordingly, the formed conductive reflective film exhibits favorable film formability and has a high diffuse reflectance. When a film is formed on a substrate of glass or the like, favorable film formability and a high diffuse reflectance can be achieved even when film formation is conducted using a vacuum deposition method such as a sputtering method, but if a vacuum deposition method such as sputtering is used to form a film on top of a second transparent conductive film that has been formed using a wet coating method, then the residual solvent within the second transparent conductive film tends to exert adverse effects on the formed conductive reflective film, meaning forming a conductive reflective film with a high reflectance is difficult.

In this manner, the composite film according to the second embodiment of the present invention yields a very high reflectance, due to an improved reflection effect, in terms of optical design, imparted by the second transparent conductive film of low refractive index formed using a wet coating method, as well as favorable film formability and high diffuse reflectance provided by the conductive reflective film.

Moreover, the average diameter of holes occurring at the contact surface of the conductive reflective film 215 on the side of the photovoltaic layer 213 is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². When a transparent substrate having a transmittance of at least 98% is used, a conductive reflective film is obtained for which a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm. This wavelength range from 500 to 1,200 nm encompasses substantially all convertible wavelengths in those cases where a polycrystalline silicon is used for the photovoltaic layer. The reason for specifying an average diameter for the holes of not more than 100 nm is that, generally, a reflectance spectrum exhibits high reflectance at the long wavelength side of the spectrum and lower reflectance at the short wavelength side, and if the average diameter of the holes exceeds 100 nm, then the inflexion point at which the reflectance starts to decrease tends to shift to a longer wavelength, meaning a favorable reflectance may become unobtainable. Furthermore, the reason for specifying an average depth for the holes of not more than 100 nm is that if the average depth of the holes exceeds 100 nm, then the gradient (slope) of the reflectance spectrum tends to increase, meaning a favorable reflectance may be unobtainable. The reason for specifying a number density for the holes of not more than 30 holes/μm² is that if the number density of the holes exceeds 30 holes/μm², then the reflectance at the long wavelength side of the spectrum tends to decrease, meaning a favorable reflectance may be unobtainable.

The average diameter of the holes is preferably within a range from 5 to 100 nm, the average depth at which the holes are positioned is preferably within a range from 5 to 100 nm, and the number density of the holes is preferably within a range from 2 to 30 holes/μm². If the values for the average diameter of the holes, the average depth at which the holes are positioned, and the number density of the holes are less than the lower limits of the above ranges, then during sintering, the elimination of gas generated by decomposition of the organic molecules of the protective agent used to chemically modify the silver nanoparticles may be inadequate, and as a result, there is a possibility that the remaining organic molecule residues may cause reductions in the conductivity and the reflectance of the conductive reflective film.

Furthermore, the conductive reflective film that constitutes part of the composite film contains one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and this facilitates the setting of the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the second transparent conductive film to not more than 100 nm, the average depth to not more than 100 nm, and the number density to not more than 30 holes/μm². Furthermore, in the conductive reflective film that constitutes part of the composite film, because the proportion of silver among the metal elements contained within the film is 75% by mass or more, a high reflectance can be achieved. If this proportion is less than 75%, then the reflectance of the conductive reflective film formed using the composition tends to decrease. Furthermore, because the thickness of the conductive reflective film that constitutes part of the composite film is within a range from 0.05 to 2.0 μm, an electrode surface resistance value of the level required of a solar cell can be obtained. Moreover, of the metal nanoparticles incorporated within the conductive reflective film that constitutes part of the composite film, because particles having a particle size within a range from 10 to 50 nm represent a number average of not less than 70%, favorable conductivity and a high reflectance are obtained.

During the formation of the conductive oxide microparticles layer that constitutes part of the second transparent conductive film, conductive oxide microparticles such as tin oxide powders of ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide: antimony-doped tin oxide), and zinc oxide powders containing one or more elements selected from the group consisting of Al, Co, Fe, In, Sn and Ti can be used favorably, and of these, ITO, ATO, AZO (Aluminum Zinc Oxide: aluminum-doped zinc oxide), IZO (Indium Zinc Oxide: indium-doped zinc oxide) and TZO (Tin Zinc Oxide: tin-doped zinc oxide) are particularly desirable. In terms of ensuring satisfactory conductivity and favorable film formability, the average particle size of the conductive oxide microparticles is preferably within a range from 2 to 100 nm, and more preferably from 5 to 50 nm.

The conductive oxide microparticles layer is formed by preparing a dispersion containing the conductive oxide microparticles dispersed within a dispersion medium, and then using a wet coating method to apply this dispersion. Examples of the dispersion medium include not only water, but also alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, glycols such as ethylene glycol, and glycol ethers such as ethyl cellosolve. In order to obtain favorable film formability, the proportion of the dispersion medium within the dispersion is preferably within a range from 50 to 99.99% by mass. The proportion of the conductive oxide microparticles within the dispersion is preferably within a range from 0.01 to 50% by mass. The reason for specifying a proportion of conductive oxide microparticles that satisfies the above range is because at proportions less than the lower limit of the above range, forming a uniform film becomes difficult, whereas if the proportion exceeds the above upper limit, forming a conductive reflective film having a thickness of not more than 500 nm becomes problematic.

A coupling agent is preferably added to the dispersion of the conductive oxide microparticles depending on the other components used. This coupling agent has the functions of improving the bonding between the conductive microparticles and the binder, and improving the adhesion between the second transparent conductive film and the photovoltaic layer or the conductive reflective film. Examples of the coupling agent include silane coupling agents, aluminum coupling agents and titanium coupling agents.

Examples of the silane coupling agents include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the aluminum coupling agents include the aluminum coupling agent containing acetoalkoxy groups illustrated below in formula (6). Furthermore, examples of the titanium coupling agents include the titanium coupling agents having dialkyl pyrophosphite groups illustrated below in formulas (7) to (9), and the titanium coupling agent having a dialkyl phosphite group illustrated below in formula (10).

The binder dispersion includes, as a binder component, either one or both of a polymeric binder and a non-polymeric binder that cure upon heating. Examples of the polymeric binder include acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers. Furthermore, the polymeric binder preferably includes one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin. Examples of the non-polymeric binder include metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates. Further, the metal contained within the metal soap, metal complex or metal alkoxide is typically aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony. These polymeric binders and non-polymeric binders cure upon heating, making it possible to form a second transparent conductive film having a low haze and low volume resistivity at low temperature. The amount of these binders within the binder dispersion is preferably within a range from 0.01 to 50% by mass, and is more preferably within a range from 0.5 to 20% by mass.

During preparation of the binder dispersion, it is preferable to use the same dispersion medium as that used in preparing the dispersion used for forming the conductive oxide microparticles layer. In order to ensure formation of a uniform film, the amount of the dispersion medium is preferably within a range from 50 to 99.99% by mass.

Furthermore, depending on the components used, the addition of a resistance reducer or a water-soluble cellulose derivative or the like may also be preferable. The resistance reducer is preferably one or more materials selected from the group consisting of mineral acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. Specific examples include a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octylate and antimony chloride, a mixture of indium nitrate and lead acetate, and a mixture of titanium acetylacetate and cobalt octylate. The amount of these resistance reducers is preferably 0.1 to 10% by mass. Addition of a water-soluble cellulose derivative improves the transparency of the formed second transparent conductive film. Specific examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount added of the water-soluble cellulose derivative is preferably within a range from 0.1 to 10% by mass.

The conductive reflective film composition used in forming the conductive reflective film of the second embodiment of the present invention is a composition composed of metal nanoparticles dispersed within a dispersion medium. The metal nanoparticles typically include at least 75% by mass, and preferably 80% by mass or more of silver nanoparticles. The reason for specifying an amount of silver nanoparticles of at least 75% by mass relative to 100% by mass of all the metal nanoparticles is because at an amount less than 75% by mass, the reflectance of the conductive reflective film formed using this composition tends to decrease. Furthermore, the silver nanoparticles are chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms.

The reason for restricting the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the metal nanoparticles to a number within a range from 1 to 3 is because if the number of carbon atoms is 4 or greater, then the protective agent becomes difficult to eliminate or decompose (detach and combust) under the heat used during the baking process, meaning a large amount of organic residue tends to remain within the film, which subsequently degenerates or degrades, causing reductions in the conductivity and reflectance of the conductive reflective film.

The silver nanoparticles include a number average of not less than 70%, and preferably not less than 75%, of silver nanoparticles having a primary particle size within a range from 10 to 50 nm. The reason for ensuring that the amount of metal nanoparticles having a primary particle size within a range from 10 to 50 nm is a number average of not less than 70% relative to 100% of all the metal nanoparticles is because if this number average is less than 70%, then the specific surface area of the metal nanoparticles increases and the proportion of the particles composed of organic matter increases, meaning that even if the organic molecules are readily eliminated or decomposed (detached and combusted) under the heat used during baking, because the amount of organic molecules is large, a large amount of organic residue tends to remain within the film, and this residue may subsequently degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film, or the particle size distribution of the metal nanoparticles may broaden considerably, making the density of the conductive reflective film prone to a reduction that causes a deterioration in the conductivity and reflectance of the conductive reflective film. Moreover, another reason for specifying a primary particle size for the metal nanoparticles of 10 to 50 nm is that statistical analyses reveal that metal nanoparticles having a primary particle size within a range from 10 to 50 nm correlate with improved stability over time.

The metal nanoparticles other than the silver nanoparticles are metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, and the amount of these metal nanoparticles other than the silver nanoparticles, relative to 100% by mass of all the metal nanoparticles, is at least 0.02% by mass but less than 25% by mass, and preferably within a range from 0.03 to 20% by mass. The reason for restricting the amount of the metal nanoparticles other than silver nanoparticles to at least 0.02% by mass but less than 25% by mass relative to 100% by mass of all the metal nanoparticles is because if the amount is less than 0.02% by mass, then although no particular problems arise, amounts within the range from 0.02 to 25% by mass still produce results for the conductivity and reflectance of the conductive reflective film following a weather resistance test (a test that involves standing for 1,000 hours in a constant temperature and humidity chamber at a temperature of 100° C. and a humidity of 50%) that display no deterioration from the results prior to the weather resistance test, whereas on the other hand, if the amount is 25% by mass or greater, then the conductivity and reflectance of the conductive reflective film immediately following baking tend to decrease, and the conductivity and reflectance of the conductive reflective film following a weather resistance test tend to be inferior to the conductivity and reflectance of the conductive reflective film prior to the weather resistance test.

Furthermore, the conductive reflective film composition includes one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils. A metal oxide, metal hydroxide, organometallic compound or silicone oil incorporated within the composition as an additive improves the adhesion to the second transparent conductive film with no loss of conductivity, either due to chemical bonding or an anchoring effect relative to the second transparent conductive film, or due to an improvement in the wettability between the metal nanoparticles and the second transparent conductive film during the baking step.

If the conductive reflective film is formed using a composition that contains none of the above metal oxides and the like, then the surface roughness of the formed conductive reflective film increases, but in order to optimize the photovoltaic conversion efficiency, specific conditions must be satisfied for the uneven shape of the surface of the conductive reflective film, and simply increasing the surface roughness does not necessarily enable the formation of a conductive reflective film surface having superior photovoltaic conversion efficiency. By appropriate adjustment of the variety and concentration and the like of the metal oxide, as described for the second embodiment of the present invention, a surface having a surface roughness that optimizes the photovoltaic conversion efficiency can be formed.

The amount of the additives is typically within a range from 0.1 to 20%, and preferably from 0.2 to 10%, of the mass of the silver nanoparticles within the metal nanoparticles. If the amount of these additives is less than 0.1%, then there is a possibility that holes having a large average diameter may be generated, and the density of the holes may increase. An amount of the additives exceeding 20% tends to exert an adverse effect on the conductivity of the formed conductive reflective film, and may result in a volume resistivity exceeding 2×10⁻⁵ Ω·cm.

As the organic polymer used as an additive, one or more polymers selected from the group consisting of polyvinylpyrrolidone (hereafter also abbreviated as PVP), PVP copolymers and water-soluble celluloses are used. Specific examples of the PVP copolymers include PVP-methacrylate copolymers, PVP-styrene copolymers and PVP-vinyl acetate copolymers. Further, examples of the water-soluble celluloses include cellulose ethers such as hydroxypropylmethylcellulose, methylcellulose and hydroxyethylmethylcellulose.

Examples of the metal oxide used as an additive include oxides or composite oxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony. Specific examples of the composite oxides include ITO, ATO and IZO.

Examples of the metal hydroxide used as an additive include hydroxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Examples of the organometallic compound used as an additive include metal soaps, metal complexes and metal alkoxides of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin. Examples of the metal soaps include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate and molybdenum acetate. Furthermore, examples of the metal complexes include a zinc acetylacetonate complex, chromium acetylacetonate complex and nickel acetylacetonate complex. Examples of the metal alkoxides include titanium isopropoxide, methyl silicate, isocyanatopropyltrimethoxysilane and aminopropyltrimethoxysilane.

Examples of the silicone oil used as an additive include both straight silicone oils and modified silicone oils. As the modified silicone oils, oils that include organic groups introduced at a portion of the side chains of a polysiloxane (side-chain type oils), oils that include organic groups introduced at both terminals of a polysiloxane (both terminal-type oils), oils that include an organic group introduced at one of the two terminals of a polysiloxane (single terminal-type oils), and oils that include organic groups introduced at a portion of the side chains and at both terminals of a polysiloxane (side-chain, both terminal-type oils) can be used. Modified silicone oils include both reactive silicone oils and unreactive silicone oils, and a combination of both types may also be used as an additive in the second embodiment of the present invention. Reactive silicone oils include amino-modified, epoxy-modified, carboxy-modified, carbinol-modified and mercapto-modified silicone oils, as well as silicone oils modified with a number of different functional groups (such as epoxy groups, amino groups and polyether groups). Unreactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, fluorine-modified, and specific hydrophilic-modified silicone oils.

The dispersion medium used in forming the conductive reflective film composition is preferably composed of an alcohol or an alcohol-containing aqueous solution. Examples of alcohols that may be used as the dispersion medium include one or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornylhexanol and erythritol. The alcohol-containing aqueous solution preferably contains, relative to 100% by mass of the entire dispersion medium, not less than 1% by mass, and preferably 2% by mass or more of water, and not less than 2% by mass, and preferably 3% by mass or more of an alcohol. For example, in those cases where the dispersion medium is composed solely of water and an alcohol, if the medium contains 2% by mass of water, then the alcohol content is 98% by mass, whereas if the medium contains 2% by mass of the alcohol, then the water content is 98% by mass. The reason for specifying a water content of not less than 1% by mass relative to 100% by mass of the entire dispersion medium is because if the water content is less than 1% by mass, then the film obtained by using a wet coating method to apply the conductive reflective film composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate. The reason for specifying an alcohol content of not less than 2% by mass relative to 100% by mass of the entire dispersion medium is because if the alcohol content is less than 2% by mass, then in a similar manner to that described above, the film obtained by using a wet coating method to apply the composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate.

Moreover, the dispersion medium, namely the protective molecules that chemically modify the surface of the metal nanoparticles, preferably contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). If a hydroxyl group (—OH) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action. If a carbonyl group (—C═O) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then in a similar manner to that described above, the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action.

Examples of the method used for producing the conductive reflective film composition include the methods outlined below.

(a) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 3

Firstly, silver nitrate is dissolved in water such as deionized water to prepare a metal salt aqueous solution. In a separate preparation, sodium citrate is dissolved in water such as deionized water to prepare an aqueous solution of sodium citrate having a concentration of 10 to 40%, and ferrous sulfate in a particulate or powder form is then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of an inert gas such as nitrogen gas, thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions. Subsequently, with the reducing agent aqueous solution undergoing constant stirring under a stream of the above inert gas, the metal salt aqueous solution described above is added dropwise to the reducing agent aqueous solution and mixed thoroughly. During this process, it is preferable that the concentrations of the solutions are altered so that the amount added of the metal salt aqueous solution is not more than 1/10th of the amount of the reducing agent aqueous solution, as this ensures that the reaction temperature can be maintained within a range from 30 to 60° C. even if the added metal salt aqueous solution is at room temperature. Further, the mixing ratio between the two aqueous solutions is preferably adjusted so that the equivalent amount of ferrous ions added as the reducing agent is three times the equivalent amount of the metal ions, in other words, (number of mols of metal ions within the metal salt aqueous solution)×(valency of metal ions)=3×(ferrous ions within the reducing agent aqueous solution). Following completion of the dropwise addition of the metal salt aqueous solution, stirring of the resulting mixed liquid is continued for a further 10 to 300 minutes, thus forming a dispersion composed of a metal colloid. This dispersion is left to stand at room temperature, the precipitated metal nanoparticle aggregates are isolated by decantation and/or centrifugal separation and the like, water such as deionized water is added to the isolated nanoparticle aggregates to form a dispersion, a demineralization treatment is conducted using ultrafiltration, and displacement washing is then performed using an alcohol, so as to achieve a metal (silver) content within a range from 2.5 to 50% by mass. Subsequently, by separating the very coarse particles using a centrifugal separator with appropriate adjustment of the centrifugal power, silver nanoparticles are prepared in which those particles having a primary particle size within a range from 10 to 50 nm represent a number average of not less than 70%. In other words, the silver nanoparticles are prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm represents a number average of not less than 70%. By using this method, a dispersion is obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the silver nanoparticles is 3.

Subsequently, the resulting dispersion is adjusted so that the final metal content (silver content) relative to 100% by mass of the dispersion is within a range from 2.5 to 95% by mass. Further, in those cases where the dispersion medium is an alcohol-containing aqueous solution, the amounts of the water and the alcohol within the medium are preferably adjusted to amounts of not less than 1% and not less than 2% respectively. Furthermore, in those cases where further additives are included within the composition, one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils are added in the desired proportions. The amount of these additives is adjusted so as to satisfy a range from 0.1 to 20% by mass relative to 100% by mass of the obtained composition. This enables a composition to be obtained in which silver nanoparticles, which have been chemically modified with a protective agent having an organic molecular main chain in which the number of carbon atoms within the carbon skeleton is 3, are dispersed within the dispersion medium.

(b) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 2

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium malate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 2.

(c) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 1

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium glycolate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 1.

(d) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to 3

Examples of the metal that constitutes the metal nanoparticles other than silver nanoparticles include gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese. With the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with chlorauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is 3.

In those cases where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to either 1 or 2, a dispersion is prepared in the same manner as either (b) or (c) above, with the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with one of the other metal salts listed above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is either 1 or 2.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles are combined as the metal nanoparticles, then for example, if the dispersion containing silver nanoparticles produced using the above method (a) is deemed the first dispersion, and the dispersion containing metal nanoparticles other than silver nanoparticles produced using the above method (d) is deemed the second dispersion, a dispersion may be prepared by mixing at least 75% by mass of the first dispersion and less than 25% by mass of the second dispersion so that the combination of the first and second dispersions totals 100% by mass. The first dispersion is not restricted to a dispersion containing silver nanoparticles produced using the above method (a), and a dispersion containing silver nanoparticles produced using the above method (b) or a dispersion containing silver nanoparticles produced using the above method (c) may also be used.

Next is a description of a method for producing a composite film according to the second embodiment of the present invention.

In the production process according to the second embodiment of the present invention, as illustrated in FIG. 3, a conductive oxide microparticles coating 224 a is first formed by using a wet coating method to apply the aforementioned dispersion, prepared by dispersing conductive oxide microparticles in a dispersion medium, to a photovoltaic layer 213 of a superstrate thin-film solar cell that has been laminated on a substrate 211 with a first transparent conductive film 212 disposed therebetween. This coating 224 a is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes.

Subsequently, the conductive oxide microparticles coating 224 a is impregnated with the aforementioned binder dispersion using a wet coating method, with the application conducted so that the entire surface of the conductive oxide microparticles coating 224 a is covered with a binder dispersion coating 224 b. Furthermore, the application is preferably conducted so that the mass of the binder component within the applied binder dispersion, relative to the total mass of microparticles contained within the applied conductive oxide microparticles coating, is a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) within a range from 0.5 to 10. If the mass ratio is less than the lower limit of the above range, then obtaining satisfactory adhesion is difficult, whereas if the mass ratio exceeds the upper limit of the range, then the surface resistance is likely to increase. This mass ratio is most preferably within a range from 0.5 to 3. The coating is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. Application of the above conductive oxide microparticles dispersion and the binder dispersion is conducted so that the thickness of the second transparent conductive film following baking is within a range from 0.01 to 0.5 μm, and preferably from 0.03 to 0.1 μm. In this manner, a transparent conductive coating 224 composed of the conductive oxide microparticles coating 224 a and the binder dispersion coating 224 b is formed.

Subsequently, the aforementioned conductive reflective film composition is applied to the transparent conductive coating 224 using a wet coating method. This application is conducted so that the thickness following baking is within a range from 0.05 to 2.0 μm, and preferably from 0.1 to 1.5 μm. The applied coating is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a conductive reflective coating 225.

The wet coating method is preferably one of a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method, although this list is not exhaustive, and any appropriate method may be used.

Spray coating is a method in which either the dispersion is converted to a fine mist using compressed air and then applied to the substrate, or the dispersion itself is pressurized and converted to a fine mist that is then applied to the substrate. Dispenser coating is a method in which, for example, the dispersion is placed inside an injector, and the dispersion is then discharged from a fine nozzle at the tip of the injector and applied to the substrate by depressing the injector piston. Spin coating is a method in which the dispersion is dripped onto a spinning substrate, and the dripped dispersion spreads out to the peripheral edges of the substrate under centrifugal force. Knife coating is a method in which a substrate that is separated from the tip of a knife by a predetermined gap is provided in a manner that enables the substrate to be moved horizontally, and the dispersion is supplied onto the substrate at a point upstream from the knife while the substrate is moved horizontally in the downstream direction. Slit coating is a method in which the dispersion is exuded from a narrow slit and coated onto the substrate. Inkjet coating is a method in which the dispersion is used to fill the ink cartridge of a commercially available inkjet printer, and the dispersion is then applied to the substrate by inkjet printing. Screen printing is a method in which a gauze is used as a patterning material, and the dispersion is transferred to the substrate through a print image formed on the gauze. Offset printing is a printing method that utilizes the water repellency of ink, wherein the dispersion applied to a plate is not adhered directly to the substrate, but is rather first transferred from the plate to a rubber sheet, before being subsequently transferred from the rubber sheet to the substrate. Die coating is a method in which a dispersion that has been supplied to a die is distributed using a manifold, and is then extruded in a thin film from a slit, and applied to the surface of a moving substrate. Die coating methods include slot coating, slide coating and curtain coating methods.

Finally, the substrate 211 having the coating 226 formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes. The reason for conducting the applications of the conductive oxide microparticles dispersion and the binder dispersion so that the thickness of the second transparent conductive film following baking is within a range from 0.01 to 0.5 μm is because if the thickness following baking is less than the lower limit of this range, then formation of a uniform film becomes difficult, whereas if the thickness exceeds the upper limit of the range, the amount of material used is more than is necessary, resulting in unnecessary material waste. The reason for conducting the application of the conductive reflective film composition so that the thickness of the conductive reflective film following baking is within a range from 0.05 to 2.0 μm is because if the thickness is less than 0.05 μm, then the surface resistance value becomes overly high, making it difficult to obtain the level of conductivity required of a solar cell electrode, whereas if the thickness exceeds 2.0 μm, then although there are no concerns in terms of the resulting properties, the amount of material used is more than is necessary, resulting in unnecessary material waste.

The reason for specifying a baking temperature within a range from 130 to 400° C. is because at temperatures lower than 130° C., a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. In contrast, if the temperature exceeds 400° C., then any merit associated with conducting the production using a low-temperature process is lost. In other words, the production costs increase, and the productivity tends to decrease. Furthermore, amorphous silicon solar cells, microcrystalline silicon solar cells, and hybrid silicon solar cells that use both these forms of silicon are particularly susceptible to heat, and a high temperature during the baking step causes a deterioration in the conversion efficiency.

The reason for specifying a baking time within a range from 5 to 60 minutes for the substrate having the coatings formed thereon is because if the baking time is less than the lower limit of this range, a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. Although lengthening the baking time beyond the upper limit of the above range has no adverse effects on the composite film properties, it results in an unnecessary increase in production costs and decrease in productivity. Moreover, the conversion efficiency of the solar cell also tends to deteriorate.

The composite film of the second embodiment of the present invention can be formed in the manner described above. In this manner, by using a wet coating method, the production process according to the second embodiment of the present invention is able to eliminate vacuum processes such as vacuum deposition and sputtering as far as possible, meaning the composite film can be produced comparatively cheaply.

Third Embodiment

As illustrated in FIG. 4, a substrate thin-film solar cell typically has a structure in which a composite film 312 is formed on top of a substrate 311, and a photovoltaic layer 313 and a first transparent conductive film (the light incident side transparent conductive film) 314 are laminated sequentially on top of the composite film 312. The composite film 312 includes a conductive reflective film 312 a formed on the substrate 311 and a second transparent conductive film 312 b formed on the conductive reflective film 312 a.

The third embodiment of the present invention relates to a composite film 312 for a substrate solar cell that is composed of two layers, namely, the conductive reflective film 312 a formed on the substrate 311 and the second transparent conductive film 312 b formed on the conductive reflective film 312 a.

In the composite film 312 of the third embodiment of the present invention, the conductive reflective film 312 a is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the substrate 311. Accordingly, the conductive reflective film 312 a exhibits favorable film formability and has a high diffuse reflectance.

Furthermore, in the composite film 312 according to the third embodiment of the present invention, the second transparent conductive film 312 b is formed by using a wet coating method to apply a transparent conductive film composition containing conductive oxide microparticles. If the second transparent conductive film is formed using a vacuum deposition method such as a sputtering method, then the refractive index of the second transparent conductive film is determined by the material used as the target material, and consequently achieving the desired refractive index is problematic for a second transparent conductive film formed using a vacuum deposition method such as sputtering. In contrast, in the case of the second transparent conductive film 312 b formed using a wet coating method, because the film is formed by applying a transparent conductive film composition that is a mixture of conductive oxide microparticles and one or more other components, a film formed using such a wet coating method is capable of realizing the desired low refractive index. The refractive index of this second transparent conductive film 312 b is typically within a range from 1.5 to 2. A second transparent conductive film 312 b having a low refractive index imparts an increased reflection effect to the adjoining conductive reflective film 312 a in terms of optical design, and therefore the conductive reflective film 312 a adjoining this second transparent conductive film 312 b has a higher reflectance than that of a conductive reflective film adjoining a second transparent conductive film having a high refractive index formed using a conventional vacuum deposition method such as sputtering.

In this manner, the composite film 312 according to the third embodiment of the present invention has an improved reflection effect, in terms of optical design, imparted by the second transparent conductive film 312 b that has a low refractive index, and a higher reflectance as a result of the favorable film formability and high diffuse reflectance provided by the conductive reflective film 312 a.

Moreover, by ensuring that the average diameter of holes occurring at the contact surface of the conductive reflective film 312 a on the side of the second transparent conductive film 312 b is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm², a conductive reflective film 312 a is obtained for which a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm when a transparent substrate having a transmittance of at least 98% is used. This wavelength range from 500 to 1,200 nm encompasses substantially all convertible wavelengths in those cases where a polycrystalline silicon is used for the photovoltaic layer. The reason for specifying an average diameter for the holes of not more than 100 nm is that, generally, a reflectance spectrum exhibits high reflectance at the long wavelength side of the spectrum and lower reflectance at the short wavelength side, and if the average diameter of the holes exceeds 100 nm, then the inflexion point at which the reflectance starts to decrease tends to shift to a longer wavelength, meaning a favorable reflectance may become unobtainable. Furthermore, the reason for specifying an average depth for the holes of not more than 100 nm is that if the average depth of the holes exceeds 100 nm, then the gradient (slope) of the reflectance spectrum tends to increase, meaning a favorable reflectance may be unobtainable. The reason for specifying a number density for the holes of not more than 30 holes/μm² is that if the number density of the holes exceeds 30 holes/μm², then the reflectance at the long wavelength side of the spectrum tends to decrease, meaning a favorable reflectance may be unobtainable.

The average diameter of the holes is preferably within a range from 5 to 100 nm, the average depth at which the holes are positioned is preferably within a range from 5 to 100 nm, and the number density of the holes is preferably within a range from 2 to 30 holes/μm². If the values for the average diameter of the holes, the average depth at which the holes are positioned, and the number density of the holes are less than the lower limits of the above ranges, then during sintering, the elimination of gas generated by decomposition of the organic molecules of the protective agent used to chemically modify the silver nanoparticles may be inadequate, and as a result, there is a possibility that the remaining organic molecule residues may cause reductions in the conductivity and the reflectance of the conductive reflective film.

The conductive reflective film that constitutes part of the composite film contains one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and this facilitates the setting of the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the second transparent conductive film to not more than 100 nm, the average depth to not more than 100 nm, and the number density to not more than 30 holes/μm². Furthermore, in the conductive reflective film that constitutes part of the composite film, because the proportion of silver among the metal elements contained within the film is 75% by mass or more, a high reflectance can be achieved. If this proportion is less than 75%, then the reflectance of the conductive reflective film formed using the composition tends to decrease. Furthermore, because the thickness of the conductive reflective film that constitutes part of the composite film is within a range from 0.05 to 2.0 μm, an electrode surface resistance value of the level required of a solar cell can be obtained. Moreover, of the metal nanoparticles incorporated within the conductive reflective film that constitutes part of the composite film, because particles having a particle size within a range from 10 to 50 nm represent a number average of not less than 70%, favorable conductivity and a high reflectance are obtained.

The transparent conductive film composition used in forming the second transparent conductive film of the third embodiment of the present invention contains conductive oxide microparticles, and is a composition in which these conductive oxide microparticles are dispersed within a dispersion medium.

As the conductive oxide microparticles incorporated within the transparent conductive film composition, tin oxide powders of ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide: antimony-doped tin oxide), and zinc oxide powders containing one or more elements selected from the group consisting of Al, Co, Fe, In, Sn and Ti are preferred, and of these, ITO, ATO, AZO (Aluminum Zinc Oxide: aluminum-doped zinc oxide), IZO (Indium Zinc Oxide: indium-doped zinc oxide) and TZO (Tin Zinc Oxide: tin-doped zinc oxide) are particularly desirable. Furthermore, the proportion of the conductive oxide microparticles within the solid fraction of the transparent conductive film composition is preferably within a range from 50 to 90% by mass. The reason for specifying a conductive oxide microparticles proportion within the above range is that at proportions less than the lower limit of the range, the conductivity tends to decrease, whereas if the proportion exceeds the upper limit of the range, the adhesion tends to deteriorate undesirably. Within the above range, a proportion of 70 to 90% by mass is particularly desirable. Furthermore, in terms of ensuring favorable stability within the dispersion medium, the average particle size of the conductive oxide microparticles is preferably within a range from 10 to 100 nm, and more preferably from 20 to 60 nm.

The transparent conductive film composition is a composition that includes either one or both of a polymeric binder and a non-polymeric binder that cure upon heating. Examples of the polymeric binder include acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers. Furthermore, the polymeric binder preferably includes one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin. Examples of the non-polymeric binder include metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates. Further, the metal contained within the metal soap, metal complex or metal alkoxide is typically aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony. These polymeric binders and non-polymeric binders cure upon heating, making it possible to form a second transparent conductive film having a low haze and low volume resistivity at low temperature. The amount of these binders, reported as a proportion of the solid fraction within the transparent conductive film composition, is preferably within a range from 5 to 50% by mass, and is more preferably within a range from 10 to 30% by mass.

A coupling agent is preferably added to the transparent conductive film composition depending on the other components used. This coupling agent has the functions of improving the bonding between the conductive microparticles and the binder, and improving the adhesion between the second transparent conductive film formed from this transparent conductive film composition and the conductive reflective film or photovoltaic layer. Examples of the coupling agent include silane coupling agents, aluminum coupling agents and titanium coupling agents.

Examples of the silane coupling agents include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the aluminum coupling agents include the aluminum coupling agent containing acetoalkoxy groups illustrated below in formula (11). Furthermore, examples of the titanium coupling agents include the titanium coupling agents having dialkyl pyrophosphite groups illustrated below in formulas (12) to (14), and the titanium coupling agent having a dialkyl phosphite group illustrated below in formula (15).

The amount of the coupling agent, reported as a proportion of the solid fraction within the transparent conductive film composition, is preferably within a range from 0.2 to 5% by mass, and is more preferably within a range from 0.5 to 2% by mass.

Examples of the dispersion medium used in forming the transparent conductive film composition include not only water, but also alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, glycols such as ethylene glycol, and glycol ethers such as ethyl cellosolve. In order to obtain favorable film formability, the proportion of the dispersion medium within the composition is preferably within a range from 80 to 99% by mass.

Furthermore, depending on the components used, the addition of a resistance reducer or a water-soluble cellulose derivative or the like may also be preferable. The resistance reducer is preferably one or more materials selected from the group consisting of mineral acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. Specific examples include a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octylate and antimony chloride, a mixture of indium nitrate and lead acetate, and a mixture of titanium acetylacetate and cobalt octylate. The amount of these resistance reducers is preferably 0.2 to 15% by mass relative to the mass of the conductive oxide powder. A water-soluble cellulose derivative is a non-ionic surfactant, but compared with other surfactants, has an extremely powerful ability to disperse the conductive oxide powder even when added in a very small amount. Furthermore, addition of a water-soluble cellulose derivative also improves the transparency of the formed second transparent conductive film. Specific examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount added of the water-soluble cellulose derivative is preferably within a range from 0.2 to 5% by mass.

The conductive reflective film composition used in forming the conductive reflective film within the composite film of the third embodiment of the present invention is a composition composed of metal nanoparticles dispersed within a dispersion medium. The metal nanoparticles typically include at least 75% by mass, and preferably 80% by mass or more of silver nanoparticles. The reason for specifying an amount of silver nanoparticles of at least 75% by mass relative to 100% by mass of all the metal nanoparticles is because at an amount less than 75% by mass, the reflectance of the conductive reflective film formed using this composition tends to decrease. Furthermore, the silver nanoparticles are chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms.

The reason for restricting the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the metal nanoparticles to a number within a range from 1 to 3 is because if the number of carbon atoms is 4 or greater, then the protective agent becomes difficult to eliminate or decompose (detach and combust) under the heat used during the baking process, meaning a large amount of organic residue tends to remain within the film, which subsequently degenerates or degrades, causing reductions in the conductivity and reflectance of the conductive reflective film.

The silver nanoparticles include a number average of not less than 70%, and preferably not less than 75%, of silver nanoparticles having a primary particle size within a range from 10 to 50 nm. The reason for ensuring that the amount of metal nanoparticles having a primary particle size within a range from 10 to 50 nm is a number average of not less than 70% relative to 100% of all the metal nanoparticles is because if this number average is less than 70%, then the specific surface area of the metal nanoparticles increases and the proportion of the particles composed of organic matter increases, meaning that even if the organic molecules are readily eliminated or decomposed (detached and combusted) under the heat used during baking, because the amount of organic molecules is large, a large amount of organic residue tends to remain within the film, and this residue may subsequently degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film, or the particle size distribution of the metal nanoparticles may broaden considerably, making the density of the conductive reflective film prone to a reduction that causes a deterioration in the conductivity and reflectance of the conductive reflective film. Moreover, another reason for specifying a primary particle size for the metal nanoparticles of 10 to 50 nm is that statistical analyses reveal that metal nanoparticles having a primary particle size within a range from 10 to 50 nm correlate with improved stability over time.

The metal nanoparticles other than the silver nanoparticles are metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, and the amount of these metal nanoparticles other than the silver nanoparticles, relative to 100% by mass of all the metal nanoparticles, is at least 0.02% by mass but less than 25% by mass, and preferably within a range from 0.03 to 20% by mass. The reason for restricting the amount of the metal nanoparticles other than silver nanoparticles to at least 0.02% by mass but less than 25% by mass relative to 100% by mass of all the metal nanoparticles is because if the amount is less than 0.02% by mass, then although no particular problems arise, amounts within the range from 0.02 to 25% by mass still produce results for the conductivity and reflectance of the conductive reflective film following a weather resistance test (a test that involves standing for 1,000 hours in a constant temperature and humidity chamber at a temperature of 100° C. and a humidity of 50%) that display no deterioration from the results prior to the weather resistance test, whereas on the other hand, if the amount is 25% by mass or greater, then the conductivity and reflectance of the conductive reflective film immediately following baking tend to decrease, and the conductivity and reflectance of the conductive reflective film following a weather resistance test tend to be inferior to the conductivity and reflectance of the conductive reflective film prior to the weather resistance test.

The conductive reflective film composition used in forming the conductive reflective film of the third embodiment of the present invention includes one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils. A metal oxide, metal hydroxide, organometallic compound or silicone oil incorporated within the composition as an additive improves the adhesion to the second transparent conductive film with no loss of conductivity, either due to chemical bonding or an anchoring effect relative to the second transparent conductive film, or due to an improvement in the wettability between the metal nanoparticles and the second transparent conductive film during the baking step.

If the conductive reflective film is formed using a composition that contains none of the above metal oxides and the like, then the surface roughness of the formed conductive reflective film increases, but in order to optimize the photovoltaic conversion efficiency, specific conditions must be satisfied for the uneven shape of the surface of the conductive reflective film, and simply increasing the surface roughness does not necessarily enable the formation of a conductive reflective film surface having superior photovoltaic conversion efficiency. By appropriate adjustment of the variety and concentration and the like of the metal oxide, as described for the third embodiment of the present invention, a surface having a surface roughness that optimizes the photovoltaic conversion efficiency can be formed.

The amount of the additives is typically within a range from 0.1 to 20%, and preferably from 0.2 to 10%, of the mass of the silver nanoparticles within the metal nanoparticles. If the amount of these additives is less than 0.1%, then there is a possibility that holes having a large average diameter may be generated, and the density of the holes may increase. An amount of the additives exceeding 20% tends to exert an adverse effect on the conductivity of the formed conductive reflective film, and may result in a volume resistivity exceeding 2×10⁻⁵ Ω·cm.

As the organic polymer used as an additive, one or more polymers selected from the group consisting of polyvinylpyrrolidone (hereafter also abbreviated as PVP), PVP copolymers and water-soluble celluloses are used. Specific examples of the PVP copolymers include PVP-methacrylate copolymers, PVP-styrene copolymers and PVP-vinyl acetate copolymers. Further, examples of the water-soluble celluloses include cellulose ethers such as hydroxypropylmethylcellulose, methylcellulose and hydroxyethylmethylcellulose.

Examples of the metal oxide used as an additive include oxides or composite oxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony. Specific examples of the composite oxides include ITO, ATO and IZO.

Examples of the metal hydroxide used as an additive include hydroxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Examples of the organometallic compound used as an additive include metal soaps, metal complexes and metal alkoxides of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin. Examples of the metal soaps include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate and molybdenum acetate. Furthermore, examples of the metal complexes include a zinc acetylacetonate complex, chromium acetylacetonate complex and nickel acetylacetonate complex. Examples of the metal alkoxides include titanium isopropoxide, methyl silicate, isocyanatopropyltrimethoxysilane and aminopropyltrimethoxysilane.

Examples of the silicone oil used as an additive include both straight silicone oils and modified silicone oils. As the modified silicone oils, oils that include organic groups introduced at a portion of the side chains of a polysiloxane (side-chain type oils), oils that include organic groups introduced at both terminals of a polysiloxane (both terminal-type oils), oils that include an organic group introduced at one of the two terminals of a polysiloxane (single terminal-type oils), and oils that include organic groups introduced at a portion of the side chains and at both terminals of a polysiloxane (side-chain, both terminal-type oils) can be used. Modified silicone oils include both reactive silicone oils and unreactive silicone oils, and a combination of both types may also be used as an additive in the third embodiment of the present invention. Reactive silicone oils include amino-modified, epoxy-modified, carboxy-modified, carbinol-modified and mercapto-modified silicone oils, as well as silicone oils modified with a number of different functional groups (such as epoxy groups, amino groups and polyether groups). Unreactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, fluorine-modified, and specific hydrophilic-modified silicone oils.

The dispersion medium used in forming the conductive reflective film composition is preferably composed of an alcohol or an alcohol-containing aqueous solution. Examples of alcohols that may be used as the dispersion medium include one or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornylhexanol and erythritol. The alcohol-Containing aqueous solution preferably contains, relative to 100% by mass of the entire dispersion medium, not less than 1% by mass, and preferably 2% by mass or more of water, and not less than 2% by mass, and preferably 3% by mass or more of an alcohol. For example, in those cases where the dispersion medium is composed solely of water and an alcohol, if the medium contains 2% by mass of water, then the alcohol content is 98% by mass, whereas if the medium contains 2% by mass of the alcohol, then the water content is 98% by mass. The reason for specifying a water content of not less than 1% by mass relative to 100% by mass of the entire dispersion medium is because if the water content is less than 1% by mass, then the film obtained by using a wet coating method to apply the conductive reflective film composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate. The reason for specifying an alcohol content of not less than 2% by mass relative to 100% by mass of the entire dispersion medium is because if the alcohol content is less than 2% by mass, then in a similar manner to that described above, the film obtained by using a wet coating method to apply the composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate.

Moreover, the dispersion medium, namely the protective molecules that chemically modify the surface of the metal nanoparticles, preferably contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). If a hydroxyl group (—OH) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action. If a carbonyl group (—C═O) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then in a similar manner to that described above, the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action.

Examples of the method used for producing the conductive reflective film composition of the third embodiment of the present invention include the methods outlined below.

(a) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 3

Firstly, silver nitrate is dissolved in water such as deionized water to prepare a metal salt aqueous solution. In a separate preparation, sodium citrate is dissolved in water such as deionized water to prepare an aqueous solution of sodium citrate having a concentration of 10 to 40%, and ferrous sulfate in a particulate or powder form is then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of an inert gas such as nitrogen gas, thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions. Subsequently, with the reducing agent aqueous solution undergoing constant stirring under a stream of the above inert gas, the metal salt aqueous solution described above is added dropwise to the reducing agent aqueous solution and mixed thoroughly. During this process, it is preferable that the concentrations of the solutions are altered so that the amount added of the metal salt aqueous solution is not more than 1/10th of the amount of the reducing agent aqueous solution, as this ensures that the reaction temperature can be maintained within a range from 30 to 60° C. even if the added metal salt aqueous solution is at room temperature. Further, the mixing ratio between the two aqueous solutions is preferably adjusted so that the equivalent amount of ferrous ions added as the reducing agent is three times the equivalent amount of the metal ions, in other words, (number of mols of metal ions within the metal salt aqueous solution)×(valency of metal ions)=3×(ferrous ions within the reducing agent aqueous solution). Following completion of the dropwise addition of the metal salt aqueous solution, stirring of the resulting mixed liquid is continued for a further 10 to 300 minutes, thus forming a dispersion composed of a metal colloid. This dispersion is left to stand at room temperature, the precipitated metal nanoparticle aggregates are isolated by decantation and/or centrifugal separation and the like, water such as deionized water is added to the isolated nanoparticle aggregates to form a dispersion, a demineralization treatment is conducted using ultrafiltration, and displacement washing is then performed using an alcohol, so as to achieve a metal (silver) content within a range from 2.5 to 50% by mass. Subsequently, by separating the very coarse particles using a centrifugal separator with appropriate adjustment of the centrifugal power, silver nanoparticles are prepared in which those particles having a primary particle size within a range from 10 to 50 nm represent a number average of not less than 70%. In other words, the silver nanoparticles are prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm represents a number average of not less than 70%. By using this method, a dispersion is obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the silver nanoparticles is 3.

Subsequently, the resulting dispersion is adjusted so that the final metal content (silver content) relative to 100% by mass of the dispersion is within a range from 2.5 to 95% by mass. Further, in those cases where the dispersion medium is an alcohol-containing aqueous solution, the amounts of the water and the alcohol within the medium are preferably adjusted to amounts of not less than 1% and not less than 2% respectively. Furthermore, in those cases where further additives are included within the composition, one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils are added in the desired proportions. The amount of these additives is adjusted so as to satisfy a range from 0.1 to 20% by mass relative to 100% by mass of the obtained composition. This enables a composition to be obtained in which silver nanoparticles, which have been chemically modified with a protective agent having an organic molecular main chain in which the number of carbon atoms within the carbon skeleton is 3, are dispersed within the dispersion medium.

(b) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 2

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium malate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 2.

(c) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 1

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium glycolate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 1.

(d) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to 3

Examples of the metal that constitutes the metal nanoparticles other than silver nanoparticles include gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese. With the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with chlorauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is 3.

In those cases where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to either 1 or 2, a dispersion is prepared in the same manner as either (b) or (c) above, with the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with one of the other metal salts listed above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is either 1 or 2.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles are combined as the metal nanoparticles, then for example, if the dispersion containing silver nanoparticles produced using the above method (a) is deemed the first dispersion, and the dispersion containing metal nanoparticles other than silver nanoparticles produced using the above method (d) is deemed the second dispersion, a dispersion may be prepared by mixing at least 75% by mass of the first dispersion and less than 25% by mass of the second dispersion so that the combination of the first and second dispersions totals 100% by mass. The first dispersion is not restricted to a dispersion containing silver nanoparticles produced using the above method (a), and a dispersion containing silver nanoparticles produced using the above method (b) or a dispersion containing silver nanoparticles produced using the above method (c) may also be used.

Next is a description of a method for producing a composite film according to the third embodiment of the present invention.

In the method for producing a composite film according to the third embodiment of the present invention, first, a wet coating method is used to apply the above conductive reflective film composition to a substrate. This application is conducted so that the thickness following baking is within a range from 0.05 to 2.0 μm, and preferably from 0.1 to 1.5 μm. Subsequently, the applied coating is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a conductive reflective coating. Next, the substrate having the conductive reflective coating formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes, thereby forming a conductive reflective film. Subsequently, a wet coating method is used to apply a transparent conductive film composition to the top of the conductive reflective film. This application is conducted so that the thickness following baking is within a range from 0.03 to 0.5 μm, and preferably from 0.05 to 0.1 μm. Subsequently, the applied coating is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a transparent conductive coating. Next, the substrate having the transparent conductive coating formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes, thereby forming a transparent conductive film.

As the above substrate, either a substrate composed of a glass, a ceramic, a metal or a polymer material, or a transparent laminate composed of two or more types of material selected from the group consisting of glass, ceramics, polymer materials, metals and silicon can be used. Examples of polymer material substrates include substrates formed from an organic polymer such as a polyimide or PET (polyethylene terephthalate).

Further, the wet coating method mentioned above is preferably one of a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method, although this list is not exhaustive, and any appropriate method may be used.

Spray coating is a method in which either the dispersion is converted to a fine mist using compressed air and then applied to the substrate, or the dispersion itself is pressurized and converted to a fine mist that is then applied to the substrate. Dispenser coating is a method in which, for example, the dispersion is placed inside an injector, and the dispersion is then discharged from a fine nozzle at the tip of the injector and applied to the substrate by depressing the injector piston. Spin coating is a method in which the dispersion is dripped onto a spinning substrate, and the dripped dispersion spreads out to the peripheral edges of the substrate under centrifugal force. Knife coating is a method in which a substrate that is separated from the tip of a knife by a predetermined gap is provided in a manner that enables the substrate to be moved horizontally, and the dispersion is supplied onto the substrate at a point upstream from the knife while the substrate is moved horizontally in the downstream direction. Slit coating is a method in which the dispersion is exuded from a narrow slit and coated onto the substrate. Inkjet coating is a method in which the dispersion is used to fill the ink cartridge of a commercially available inkjet printer, and the dispersion is then applied to the substrate by inkjet printing. Screen printing is a method in which a gauze is used as a patterning material, and the dispersion is transferred to the substrate through a print image formed on the gauze. Offset printing is a printing method that utilizes the water repellency of ink, wherein the dispersion applied to a plate is not adhered directly to the substrate, but is rather first transferred from the plate to a rubber sheet, before being subsequently transferred from the rubber sheet to the substrate. Die coating is a method in which a dispersion that has been supplied to a die is distributed using a manifold, and is then extruded in a thin film from a slit, and applied to the surface of a moving substrate. Die coating methods include slot coating, slide coating and curtain coating methods.

The reason for conducting the application of the conductive reflective film composition so that the thickness of the conductive reflective film following baking is within a range from 0.05 to 2.0 μm is because if the thickness is less than 0.05 μm, then the surface resistance value becomes overly high, making it difficult to obtain the level of conductivity required of a solar cell electrode, whereas if the thickness exceeds 2.0 μm, then although there are no concerns in terms of the resulting properties, the amount of material used is more than is necessary, resulting in unnecessary material waste. Furthermore, the reason for conducting the application of the transparent conductive film composition so that the thickness of the second transparent conductive film following baking is within a range from 0.03 to 0.5 μm is because if the thickness following baking is less than 0.03 μm or greater than 0.5 μm, then a satisfactory improvement in the reflection cannot be obtained.

The reason for specifying a baking temperature within a range from 130 to 400° C. is because at temperatures lower than 130° C., a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. In contrast, if the temperature exceeds 400° C., then any merit associated with conducting the production using a low-temperature process is lost. In other words, the production costs increase, and the productivity tends to decrease. Furthermore, amorphous silicon solar cells, microcrystalline silicon solar cells, and hybrid silicon solar cells that use both these forms of silicon are particularly susceptible to heat, and a high temperature during the baking step causes a deterioration in the conversion efficiency.

The reason for specifying a baking time within a range from 5 to 60 minutes for the substrate having the coatings formed thereon is because if the baking time is less than the lower limit of this range, then a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. Although lengthening the baking time beyond the upper limit of the above range has no adverse effects on the composite film properties, it results in an unnecessary increase in production costs and decrease in productivity. Moreover, the conversion efficiency of the solar cell also tends to deteriorate.

The composite film of the third embodiment of the present invention can be formed in the manner described above. In this manner, by using a wet coating method, the production process according to the third embodiment of the present invention is able to eliminate vacuum processes such as vacuum deposition and sputtering as far as possible, meaning the composite film can be produced comparatively cheaply.

Fourth Embodiment

A substrate thin-film solar cell typically has a structure in which a composite film 414 is provided on top of a substrate 411, and a photovoltaic layer 415 and a first transparent conductive film (the light incident side transparent conductive film) 416 are laminated sequentially on top of the composite film 414. The composite film 414 includes a conductive reflective film 412 formed on the substrate 411 and a second transparent conductive film 413 formed on the conductive reflective film 412.

The fourth embodiment of the present invention relates to a composite film for a substrate solar cell that is composed of the conductive reflective film formed on the substrate of the substrate solar cell and the second transparent conductive film formed on top of this conductive reflective film.

FIG. 5 is a diagram that schematically illustrates a cross-section of a composite according to the fourth embodiment of the present invention. As illustrated in FIG. 5, the special features of the structure of the composite film of the fourth embodiment of the present invention are (1) that the conductive reflective film 412 is formed by forming a conductive reflective coating by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the substrate 411, and then baking the conductive reflective coating, (2) that the conductive reflective film 412 has a thickness of 0.05 to 2.0 μm, (3) that the second transparent conductive film 413 is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to the conductive reflective coating, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, and (4) that the second transparent conductive film 413 has a thickness of 0.01 to 0.5 μm in a state where the entire surface of a conductive oxide microparticles layer 413 a is covered with a binder layer 413 b.

In the composite film 414 of the fourth embodiment of the present invention, the conductive reflective film 412 is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the substrate 411. Accordingly, the formed conductive reflective film 412 exhibits favorable film formability and has a high diffuse reflectance.

Furthermore, in the composite film 414 of the fourth embodiment of the present invention, the second transparent conductive film 413 is formed using a wet coating method. If the second transparent conductive film is formed using a vacuum deposition method such as a sputtering method, then the refractive index of the second transparent conductive film is determined by the material used as the target material, and consequently achieving the desired refractive index is problematic for a second transparent conductive film formed using a vacuum deposition method such as sputtering. In contrast, in the case of a second transparent conductive film formed using a wet coating method, because the film is generally formed by applying a composition that is a mixture of conductive oxide microparticles and one or more other components, a film formed using such a wet coating method is capable of realizing the desired low refractive index by appropriate adjustment of the components within the composition. The refractive index of this second transparent conductive film is typically within a range from 1.5 to 2. A second transparent conductive film having a low refractive index imparts an increased reflection effect to the adjoining conductive reflective film in terms of optical design, and therefore a conductive reflective film adjoining a second transparent conductive film formed using a wet coating method exhibits a higher reflectance than that obtainable for a conductive reflective film adjoining a second transparent conductive film having a high refractive index formed using a conventional vacuum deposition method such as sputtering.

One example of a second transparent conductive film formed using a wet coating method is a simple second transparent conductive film formed by applying a composition prepared by combining conductive oxide microparticles and a binder component, and subsequently baking the applied coating. On the other hand, the second transparent conductive film in the composite film according to the fourth embodiment of the present invention is formed by first forming a coating of conductive oxide microparticles containing no binder component on the conductive reflective coating, subsequently applying a binder dispersion containing no conductive oxide microparticles to the layer of the conductive oxide microparticles, and then performing baking at a predetermined temperature. In other words, as illustrated in FIG. 5, the second transparent conductive film of the composite film according to the fourth embodiment of the present invention has the binder layer 413 b that contains no conductive oxide microparticles as the upper layer. Further, the lower layer near the interface with the conductive reflective film 412 is composed of the conductive oxide microparticles layer 413 a, which is totally covered with the binder layer 413 b, and contains a portion of the binder dispersion that impregnates the conductive oxide microparticles layer when the binder dispersion is applied. Upon baking, a portion of the particles within this conductive oxide microparticles layer 413 a undergo sintering, thereby ensuring a high degree of conductivity.

In the composite film of the fourth embodiment of the present invention, by forming the second transparent conductive film with the structure described above, the level of adhesion with the underlying conductive reflective film can be improved compared with a composite film having a simple second transparent conductive film formed using a composition containing both the conductive oxide microparticles and a binder component. Furthermore, because the composite film is formed with the entire surface of the conductive oxide microparticles layer covered with the binder layer, change in the film over time is minimal.

In this manner, the composite film according to the fourth embodiment of the present invention yields a very high reflectance, due to an improved reflection effect, in terms of optical design, imparted by the second transparent conductive film of low refractive index formed using a wet coating method, as well as favorable film formability and high diffuse reflectance provided by the conductive reflective film.

Furthermore, the average diameter of holes occurring at the contact surface of the conductive reflective film 412 on the side of the second transparent conductive film 413 is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². When a transparent substrate having a transmittance of at least 98% is used, a conductive reflective film is obtained for which a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm. This wavelength range from 500 to 1,200 nm encompasses substantially all convertible wavelengths in those cases where a polycrystalline silicon is used for the photovoltaic layer. The reason for specifying an average diameter for the holes of not more than 100 nm is that, generally, a reflectance spectrum exhibits high reflectance at the long wavelength side of the spectrum and lower reflectance at the short wavelength side, and if the average diameter of the holes exceeds 100 nm, then the inflexion point at which the reflectance starts to decrease tends to shift to a longer wavelength, meaning a favorable reflectance may become unobtainable. Furthermore, the reason for specifying an average depth for the holes of not more than 100 nm is that if the average depth of the holes exceeds 100 nm, then the gradient (slope) of the reflectance spectrum tends to increase, meaning a favorable reflectance may be unobtainable. The reason for specifying a number density for the holes of not more than 30 holes/μm² is that if the number density of the holes exceeds 30 holes/μm², then the reflectance at the long wavelength side of the spectrum tends to decrease, meaning a favorable reflectance may be unobtainable.

The average diameter of the holes is preferably within a range from 5 to 100 nm, the average depth at which the holes are positioned is preferably within a range from 5 to 100 nm, and the number density of the holes is preferably within a range from 2 to 30 holes/μm². If the values for the average diameter of the holes, the average depth at which the holes are positioned, and the number density of the holes are less than the lower limits of the above ranges, then during sintering, the elimination of gas generated by decomposition of the organic molecules of the protective agent used to chemically modify the silver nanoparticles may be inadequate, and as a result, there is a possibility that the remaining organic molecule residues may cause reductions in the conductivity and the reflectance of the conductive reflective film.

Furthermore, the conductive reflective film that constitutes part of the composite film contains one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and this facilitates the setting of the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the second transparent conductive film to not more than 100 nm, the average depth to not more than 100 nm, and the number density to not more than 30 holes/μm². Furthermore, in the conductive reflective film that constitutes part of the composite film, because the proportion of silver among the metal elements contained within the film is 75% by mass or more, a high reflectance can be achieved. If this proportion is less than 75%, then the reflectance of the conductive reflective film formed using the composition tends to decrease. Furthermore, because the thickness of the conductive reflective film that constitutes part of the composite film is within a range from 0.05 to 2.0 μm, an electrode surface resistance value of the level required of a solar cell can be obtained. Moreover, of the metal nanoparticles incorporated within the conductive reflective film that constitutes part of the composite film, because particles having a particle size within a range from 10 to 50 nm represent a number average of not less than 70%, favorable conductivity and a high reflectance are obtained.

During the formation of the conductive oxide microparticles layer that constitutes part of the second transparent conductive film, conductive oxide microparticles such as tin oxide powders of ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide: antimony-doped tin oxide), and zinc oxide powders containing one or more elements selected from the group consisting of Al, Co, Fe, In, Sn and Ti can be used favorably, and of these, ITO, ATO, AZO (Aluminum Zinc Oxide: aluminum-doped zinc oxide), IZO (Indium Zinc Oxide: indium-doped zinc oxide) and TZO (Tin Zinc Oxide: tin-doped zinc oxide) are particularly desirable. In terms of ensuring satisfactory conductivity and favorable film formability, the average particle size of the conductive oxide microparticles is preferably within a range from 2 to 100 nm, and more preferably from 5 to 50 nm.

The conductive oxide microparticles layer is formed by preparing a dispersion containing the conductive oxide microparticles dispersed within a dispersion medium, and then using a wet coating method to apply this dispersion. Examples of the dispersion medium include not only water, but also alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, glycols such as ethylene glycol, and glycol ethers such as ethyl cellosolve. In order to obtain favorable film formability, the proportion of the dispersion medium within the dispersion is preferably within a range from 50 to 99.99% by mass. The proportion of the conductive oxide microparticles within the dispersion is preferably within a range from 0.01 to 50% by mass. The reason for specifying a proportion of conductive oxide microparticles that satisfies the above range is because at proportions less than the lower limit of the above range, forming a uniform film becomes difficult, whereas if the proportion exceeds the above upper limit, forming a conductive reflective film having a thickness of not more than 100 nm becomes problematic.

A coupling agent is preferably added to the dispersion of the conductive oxide microparticles depending on the other components used. This coupling agent has the functions of improving the bonding between the conductive microparticles and the binder, and improving the adhesion between the second transparent conductive film and the conductive reflective film or the photovoltaic layer. Examples of the coupling agent include silane coupling agents, aluminum coupling agents and titanium coupling agents.

Examples of the silane coupling agents include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the aluminum coupling agents include the aluminum coupling agent containing acetoalkoxy groups illustrated below in formula (16). Furthermore, examples of the titanium coupling agents include the titanium coupling agents having dialkyl pyrophosphite groups illustrated below in formulas (17) to (19), and the titanium coupling agent having a dialkyl phosphite group illustrated below in formula (20).

The binder dispersion includes, as a binder component, either one or both of a polymeric binder and a non-polymeric binder that cure upon heating. Examples of the polymeric binder include acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers. Furthermore, the polymeric binder preferably includes one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin. Examples of the non-polymeric binder include metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates. Further, the metal contained within the metal soap, metal complex or metal alkoxide is typically aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony. These polymeric binders and non-polymeric binders cure upon heating, making it possible to form a second transparent conductive film having a low haze and low volume resistivity at low temperature. The amount of these binders within the binder dispersion is preferably within a range from 0.01 to 50% by mass, and is more preferably within a range from 0.5 to 20% by mass.

During preparation of the binder dispersion, it is preferable to use the same dispersion medium as that used in preparing the dispersion used for forming the conductive oxide microparticles layer. In order to ensure formation of a uniform film, the amount of the dispersion medium is preferably within a range from 50 to 99.99% by mass.

Furthermore, depending on the components used, the addition of a resistance reducer or a water-soluble cellulose derivative or the like may also be preferable. The resistance reducer is preferably one or more materials selected from the group consisting of mineral acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. Specific examples include a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octylate and antimony chloride, a mixture of indium nitrate and lead acetate, and a mixture of titanium acetylacetate and cobalt octylate. The amount of these resistance reducers is preferably 0.1 to 10% by mass. Addition of a water-soluble cellulose derivative improves the transparency of the formed second transparent conductive film. Specific examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount added of the water-soluble cellulose derivative is preferably within a range from 0.1 to 10% by mass.

The conductive reflective film composition used in forming the conductive reflective film of the fourth embodiment of the present invention is a composition composed of metal nanoparticles dispersed within a dispersion medium. The metal nanoparticles typically include at least 75% by mass, and preferably 80% by mass or more of silver nanoparticles. The reason for specifying an amount of silver nanoparticles of at least 75% by mass relative to 100% by mass of all the metal nanoparticles is because at an amount less than 75% by mass, the reflectance of the conductive reflective film formed using this composition tends to decrease. Furthermore, the silver nanoparticles are chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms.

The reason for restricting the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the metal nanoparticles to a number within a range from 1 to 3 is because if the number of carbon atoms is 4 or greater, then the protective agent becomes difficult to eliminate or decompose (detach and combust) under the heat used during the baking process, meaning a large amount of organic residue tends to remain within the film, which subsequently degenerates or degrades, causing reductions in the conductivity and reflectance of the conductive reflective film.

The silver nanoparticles include a number average of not less than 70%, and preferably not less than 75%, of silver nanoparticles having a primary particle size within a range from 10 to 50 nm. The reason for ensuring that the amount of metal nanoparticles having a primary particle size within a range from 10 to 50 nm is a number average of not less than 70% relative to 100% of all the metal nanoparticles is because if this number average is less than 70%, then the specific surface area of the metal nanoparticles increases and the proportion of the particles composed of organic matter increases, meaning that even if the organic molecules are readily eliminated or decomposed (detached and combusted) under the heat used during baking, because the amount of organic molecules is large, a large amount of organic residue tends to remain within the film, and this residue may subsequently degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film, or the particle size distribution of the metal nanoparticles may broaden considerably, making the density of the conductive reflective film prone to a reduction that causes a deterioration in the conductivity and reflectance of the conductive reflective film. Moreover, another reason for specifying a primary particle size for the metal nanoparticles of 10 to 50 nm is that statistical analyses reveal that metal nanoparticles having a primary particle size within a range from 10 to 50 nm correlate with improved stability over time.

The metal nanoparticles other than the silver nanoparticles are metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, and the amount of these metal nanoparticles other than the silver nanoparticles, relative to 100% by mass of all the metal nanoparticles, is at least 0.02% by mass but less than 25% by mass, and preferably within a range from 0.03 to 20% by mass. The reason for restricting the amount of the metal nanoparticles other than silver nanoparticles to at least 0.02% by mass but less than 25% by mass relative to 100% by mass of all the metal nanoparticles is because if the amount is less than 0.02% by mass, then although no particular problems arise, amounts within the range from 0.02 to 25% by mass still produce results for the conductivity and reflectance of the conductive reflective film following a weather resistance test (a test that involves standing for 1,000 hours in a constant temperature and humidity chamber at a temperature of 100° C. and a humidity of 50%) that display no deterioration from the results prior to the weather resistance test, whereas on the other hand, if the amount is 25% by mass or greater, then the conductivity and reflectance of the conductive reflective film immediately following baking tend to decrease, and the conductivity and reflectance of the conductive reflective film following a weather resistance test tend to be inferior to the conductivity and reflectance of the conductive reflective film prior to the weather resistance test.

Furthermore, the conductive reflective film composition includes one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils. A metal oxide, metal hydroxide, organometallic compound or silicone oil incorporated within the composition as an additive improves the adhesion to the second transparent conductive film with no loss of conductivity, either due to chemical bonding or an anchoring effect relative to the second transparent conductive film, or due to an improvement in the wettability between the metal nanoparticles and the second transparent conductive film during the baking step.

If the conductive reflective film is formed using a composition that contains none of the above metal oxides and the like, then the surface roughness of the formed conductive reflective film increases, but in order to optimize the photovoltaic conversion efficiency, specific conditions must be satisfied for the uneven shape of the surface of the conductive reflective film, and simply increasing the surface roughness does not necessarily enable the formation of a conductive reflective film surface having superior photovoltaic conversion efficiency. By appropriate adjustment of the variety and concentration and the like of the metal oxide, as described for the fourth embodiment of the present invention, a surface having a surface roughness that optimizes the photovoltaic conversion efficiency can be formed.

The amount of the additives is typically within a range from 0.1 to 20%, and preferably from 0.2 to 10%, of the mass of the silver nanoparticles within the metal nanoparticles. If the amount of these additives is less than 0.1%, then there is a possibility that holes having a large average diameter may be generated, and the density of the holes may increase. An amount of the additives exceeding 20% tends to exert an adverse effect on the conductivity of the formed conductive reflective film, and may result in a volume resistivity exceeding 2×10⁻⁵ Ω·cm.

As the organic polymer used as an additive, one or more polymers selected from the group consisting of polyvinylpyrrolidone (hereafter also abbreviated as PVP), PVP copolymers and water-soluble celluloses are used. Specific examples of the PVP copolymers include PVP-methacrylate copolymers, PVP-styrene copolymers and PVP-vinyl acetate copolymers. Further, examples of the water-soluble celluloses include cellulose ethers such as hydroxypropylmethylcellulose, methylcellulose and hydroxyethylmethylcellulose.

Examples of the metal oxide used as an additive include oxides or composite oxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony. Specific examples of the composite oxides include ITO, ATO and IZO.

Examples of the metal hydroxide used as an additive include hydroxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Examples of the organometallic compound used as an additive include metal soaps, metal complexes and metal alkoxides of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin. Examples of the metal soaps include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate and molybdenum acetate. Furthermore, examples of the metal complexes include a zinc acetylacetonate complex, chromium acetylacetonate complex and nickel acetylacetonate complex. Examples of the metal alkoxides include titanium isopropoxide, methyl silicate, isocyanatopropyltrimethoxysilane and aminopropyltrimethoxysilane.

Examples of the silicone oil used as an additive include both straight silicone oils and modified silicone oils. As the modified silicone oils, oils that include organic groups introduced at a portion of the side chains of a polysiloxane (side-chain type oils), oils that include organic groups introduced at both terminals of a polysiloxane (both terminal-type oils), oils that include an organic group introduced at one of the two terminals of a polysiloxane (single terminal-type oils), and oils that include organic groups introduced at a portion of the side chains and at both terminals of a polysiloxane (side-chain, both terminal-type oils) can be used. Modified silicone oils include both reactive silicone oils and unreactive silicone oils, and a combination of both types may also be used as an additive in the fourth embodiment of the present invention. Reactive silicone oils include amino-modified, epoxy-modified, carboxy-modified, carbinol-modified and mercapto-modified silicone oils, as well as silicone oils modified with a number of different functional groups (such as epoxy groups, amino groups and polyether groups). Unreactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, fluorine-modified, and specific hydrophilic-modified silicone oils.

The dispersion medium used in forming the conductive reflective film composition is preferably composed of an alcohol or an alcohol-containing aqueous solution. Examples of alcohols that may be used as the dispersion medium include one or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornylhexanol and erythritol. The alcohol-containing aqueous solution preferably contains, relative to 100% by mass of the entire dispersion medium, not less than 1% by mass, and preferably 2% by mass or more of water, and not less than 2% by mass, and preferably 3% by mass or more of an alcohol. For example, in those cases where the dispersion medium is composed solely of water and an alcohol, if the medium contains 2% by mass of water, then the alcohol content is 98% by mass, whereas if the medium contains 2% by mass of the alcohol, then the water content is 98% by mass. The reason for specifying a water content of not less than 1% by mass relative to 100% by mass of the entire dispersion medium is because if the water content is less than 1% by mass, then the film obtained by using a wet coating method to apply the conductive reflective film composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate. The reason for specifying an alcohol content of not less than 2% by mass relative to 100% by mass of the entire dispersion medium is because if the alcohol content is less than 2% by mass, then in a similar manner to that described above, the film obtained by using a wet coating method to apply the composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate.

Moreover, the dispersion medium, namely the protective molecules that chemically modify the surface of the metal nanoparticles, preferably contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). If a hydroxyl group (—OH) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action. If a carbonyl group (—C═O) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then in a similar manner to that described above, the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action.

Examples of the method used for producing the conductive reflective film composition include the methods outlined below.

(a) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 3

Firstly, silver nitrate is dissolved in water such as deionized water to prepare a metal salt aqueous solution. In a separate preparation, sodium citrate is dissolved in water such as deionized water to prepare an aqueous solution of sodium citrate having a concentration of 10 to 40%, and ferrous sulfate in a particulate or powder form is then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of an inert gas such as nitrogen gas, thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions. Subsequently, with the reducing agent aqueous solution undergoing constant stirring under a stream of the above inert gas, the metal salt aqueous solution described above is added dropwise to the reducing agent aqueous solution and mixed thoroughly. During this process, it is preferable that the concentrations of the solutions are altered so that the amount added of the metal salt aqueous solution is not more than 1/10th of the amount of the reducing agent aqueous solution, as this ensures that the reaction temperature can be maintained within a range from 30 to 60° C. even if the added metal salt aqueous solution is at room temperature. Further, the mixing ratio between the two aqueous solutions is preferably adjusted so that the equivalent amount of ferrous ions added as the reducing agent is three times the equivalent amount of the metal ions, in other words, (number of mols of metal ions within the metal salt aqueous solution)×(valency of metal ions)=3×(ferrous ions within the reducing agent aqueous solution). Following completion of the dropwise addition of the metal salt aqueous solution, stirring of the resulting mixed liquid is continued for a further 10 to 300 minutes, thus forming a dispersion composed of a metal colloid. This dispersion is left to stand at room temperature, the precipitated metal nanoparticle aggregates are isolated by decantation and/or centrifugal separation and the like, water such as deionized water is added to the isolated nanoparticle aggregates to form a dispersion, a demineralization treatment is conducted using ultrafiltration, and displacement washing is then performed using an alcohol, so as to achieve a metal (silver) content within a range from 2.5 to 50% by mass. Subsequently, by separating the very coarse particles using a centrifugal separator with appropriate adjustment of the centrifugal power, silver nanoparticles are prepared in which those particles having a primary particle size within a range from 10 to 50 nm represent a number average of not less than 70%. In other words, the silver nanoparticles are prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm represents a number average of not less than 70%. By using this method, a dispersion is obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the silver nanoparticles is 3.

Subsequently, the resulting dispersion is adjusted so that the final metal content (silver content) relative to 100% by mass of the dispersion is within a range from 2.5 to 95% by mass. Further, in those cases where the dispersion medium is an alcohol-containing aqueous solution, the amounts of the water and the alcohol within the medium are preferably adjusted to amounts of not less than 1% and not less than 2% respectively. Furthermore, in those cases where further additives are included within the composition, one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils are added in the desired proportions. The amount of these additives is adjusted so as to satisfy a range from 0.1 to 20% by mass relative to 100% by mass of the obtained composition. This enables a composition to be obtained in which silver nanoparticles, which have been chemically modified with a protective agent having an organic molecular main chain in which the number of carbon atoms within the carbon skeleton is 3, are dispersed within the dispersion medium.

(b) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 2

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium malate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 2.

(c) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 1

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium glycolate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 1.

(d) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to 3

Examples of the metal that constitutes the metal nanoparticles other than silver nanoparticles include gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese. With the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with chlorauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is 3.

In those cases where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to either 1 or 2, a dispersion is prepared in the same manner as either (b) or (c) above, with the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with one of the other metal salts listed above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is either 1 or 2.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles are combined as the metal nanoparticles, then for example, if the dispersion containing silver nanoparticles produced using the above method (a) is deemed the first dispersion, and the dispersion containing metal nanoparticles other than silver nanoparticles produced using the above method (d) is deemed the second dispersion, a dispersion may be prepared by mixing at least 75% by mass of the first dispersion and less than 25% by mass of the second dispersion so that the combination of the first and second dispersions totals 100% by mass. The first dispersion is not restricted to a dispersion containing silver nanoparticles produced using the above method (a), and a dispersion containing silver nanoparticles produced using the above method (b) or a dispersion containing silver nanoparticles produced using the above method (c) may also be used.

Next is a description of a method for producing a composite film according to the fourth embodiment of the present invention.

In the production process according to the fourth embodiment of the present invention, first, a wet coating method is used to apply the above conductive reflective film composition to the substrate 411. This application is conducted so that the thickness following baking is within a range from 0.05 to 2.0 μm, and preferably from 0.1 to 1.5 μm. The applied coating is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of a conductive reflective coating. Next, the substrate 411 having the conductive reflective coating formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes, thereby forming the conductive reflective film 412.

Subsequently, as illustrated in FIG. 6, a conductive oxide microparticles coating 423 a is formed by using a wet coating method to apply the aforementioned dispersion, prepared by dispersing conductive oxide microparticles in a dispersion medium, to the conductive reflective film 412. This coating 423 a is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. Next, the conductive oxide microparticles coating 423 a is impregnated with the aforementioned binder dispersion using a wet coating method, with the application conducted so that the entire surface of the conductive oxide microparticles coating 423 a is covered with a binder dispersion coating 423 b. Furthermore, the application is preferably conducted so that the mass of the binder component within the applied binder dispersion, relative to the total mass of microparticles contained within the applied conductive oxide microparticles coating, is a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) within a range from 0.5 to 10. If this mass ratio is less than the lower limit of the above range, then obtaining satisfactory adhesion is difficult, whereas if the mass ratio exceeds the upper limit of the range, then the surface resistance is likely to increase. This mass ratio is most preferably within a range from 0.5 to 3. The coating is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. Application of the above conductive oxide microparticles dispersion and the binder dispersion is conducted so that the thickness of the formed second transparent conductive film following baking is within a range from 0.01 to 0.5 μm, and preferably from 0.03 to 0.1 μm. In this manner, a transparent conductive coating 423 composed of the conductive oxide microparticles coating 423 a and the binder dispersion coating 423 b is formed. Subsequently, the substrate 411 having the transparent conductive coating 423 formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes, thereby forming the second conductive reflective film.

The wet coating method is preferably one of a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method, although this list is not exhaustive, and any appropriate method may be used.

Spray coating is a method in which either the dispersion is converted to a fine mist using compressed air and then applied to the substrate, or the dispersion itself is pressurized and converted to a fine mist that is then applied to the substrate. Dispenser coating is a method in which, for example, the dispersion is placed inside an injector, and the dispersion is then discharged from a fine nozzle at the tip of the injector and applied to the substrate by depressing the injector piston. Spin coating is a method in which the dispersion is dripped onto a spinning substrate, and the dripped dispersion spreads out to the peripheral edges of the substrate under centrifugal force. Knife coating is a method in which a substrate that is separated from the tip of a knife by a predetermined gap is provided in a manner that enables the substrate to be moved horizontally, and the dispersion is supplied onto the substrate at a point upstream from the knife while the substrate is moved horizontally in the downstream direction. Slit coating is a method in which the dispersion is exuded from a narrow slit and coated onto the substrate. Inkjet coating is a method in which the dispersion is used to fill the ink cartridge of a commercially available inkjet printer, and the dispersion is then applied to the substrate by inkjet printing. Screen printing is a method in which a gauze is used as a patterning material, and the dispersion is transferred to the substrate through a print image formed on the gauze. Offset printing is a printing method that utilizes the water repellency of ink, wherein the dispersion applied to a plate is not adhered directly to the substrate, but is rather first transferred from the plate to a rubber sheet, before being subsequently transferred from the rubber sheet to the substrate. Die coating is a method in which a dispersion that has been supplied to a die is distributed using a manifold, and is then extruded in a thin film from a slit, and applied to the surface of a moving substrate. Die coating methods include slot coating, slide coating and curtain coating methods.

The reason for conducting the application of the conductive reflective film composition so that the thickness of the conductive reflective film following baking is within a range from 0.05 to 2.0 μm is because if the thickness is less than 0.05 μm, then the surface resistance value becomes overly high, making it difficult to obtain the level of conductivity required of a solar cell electrode, whereas if the thickness exceeds 2.0 μm, then although there are no concerns in terms of the resulting properties, the amount of material used is more than is necessary, resulting in unnecessary material waste. Furthermore, the reason for conducting the application of the dispersion of the conductive oxide microparticles and the binder dispersion so that the thickness of the second transparent conductive film following baking is within a range from 0.01 to 0.5 is because if the thickness following baking is less than 0.01 μm, then formation of a uniform film becomes difficult, whereas if the thickness exceeds 0.5 μm, then the amount of material used is more than is necessary, resulting in unnecessary material waste.

The reason for specifying a baking temperature within a range from 130 to 400° C. is because at temperatures lower than 130° C., a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. In contrast, if the temperature exceeds 400° C., then any merit associated with conducting the production using a low-temperature process is lost. In other words, the production costs increase, and the productivity tends to decrease. Furthermore, amorphous silicon solar cells, microcrystalline silicon solar cells, and hybrid silicon solar cells that use both these forms of silicon are particularly susceptible to heat, and a high temperature during the baking step causes a deterioration in the conversion efficiency.

The reason for specifying a baking time within a range from 5 to 60 minutes for the substrate having the coatings formed thereon is because if the baking time is less than the lower limit of this range, then a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. Although lengthening the baking time beyond the upper limit of the above range has no adverse effects on the composite film properties, it results in an unnecessary increase in production costs and decrease in productivity. Moreover, the conversion efficiency of the solar cell also tends to deteriorate.

The composite film of the fourth embodiment of the present invention can be formed in the manner described above. In this manner, by using a wet coating method, the production process according to the fourth embodiment of the present invention is able to eliminate vacuum processes such as vacuum deposition and sputtering as far as possible, meaning the composite film can be produced comparatively cheaply.

Fifth Embodiment

A superstrate thin-film solar cell typically has a structure in which a first transparent conductive film (the light incident side transparent conductive film) and a photovoltaic layer are laminated sequentially on top of a substrate, a second transparent conductive film is formed on top of the photovoltaic layer, and a conductive reflective film is then formed on top of the second transparent conductive film.

The fifth embodiment of the present invention relates to a composite film for a superstrate solar cell that has a second transparent conductive film formed on a photovoltaic layer of the superstrate solar cell, and a conductive reflective film formed on top of the second transparent conductive film.

FIG. 7 is a diagram that schematically illustrates a cross-section of a composite film 516 according to a fifth embodiment of the present invention. As illustrated in FIG. 7, the special features of the structure of the composite film of the fifth embodiment of the present invention are (1) that a second transparent conductive film 514 is formed by forming a coating of conductive oxide microparticles by using a wet coating method to apply a dispersion of the conductive oxide microparticles to a photovoltaic layer 513, impregnating the coating of the conductive oxide microparticles with a binder dispersion using a wet coating method, and subsequently performing baking, and (2) that the second transparent conductive film 514 has a first layer 514 a containing a binder component on top of the photovoltaic layer 513, and a second layer 514 b containing no binder component in which 1 to 30% of the volume of the first layer 514 a protrudes from the first layer 514 a.

If the second transparent conductive film is formed using a vacuum deposition method such as a sputtering method, then the refractive index of the second transparent conductive film is determined by the material used as the target material, and consequently achieving the desired refractive index is problematic for a second transparent conductive film formed using a vacuum deposition method such as sputtering. In contrast, in the case of a second transparent conductive film formed using a wet coating method, because the film is generally formed by applying a composition that is a mixture of conductive oxide microparticles and one or more other components, a film formed using such a wet coating method is capable of realizing the desired low refractive index by appropriate adjustment of the components within the composition. The refractive index of this second transparent conductive film is typically within a range from 1.5 to 2. A second transparent conductive film having a low refractive index imparts an increased reflection effect to the adjoining conductive reflective film in terms of optical design, and therefore a conductive reflective film adjoining a second transparent conductive film formed using a wet coating method exhibits a higher reflectance than that obtainable for a conductive reflective film adjoining a second transparent conductive film having a high refractive index formed using a conventional vacuum deposition method such as sputtering.

One example of a second transparent conductive film formed using a wet coating method is a simple second transparent conductive film formed by applying a composition prepared by combining conductive oxide microparticles and a binder component, and subsequently baking the applied coating. On the other hand, the second transparent conductive film in the composite film according to the fifth embodiment of the present invention is formed by first forming a coating of conductive oxide microparticles containing no binder component on the photovoltaic layer, and then impregnating this coating of conductive oxide microparticles with a binder dispersion containing no conductive oxide microparticles, so that the subsequent baking is performed with a portion of the coating of the conductive oxide microparticles protruding from the applied binder dispersion. In other words, as illustrated in FIG. 7, in the second transparent conductive film 514 within the composite film according to the fifth embodiment of the present invention, the lower layer is formed from the first layer 514 a, which is a conductive oxide microparticles layer containing a binder component, and the upper layer is formed from the second layer 514 b, which is a conductive oxide microparticles layer containing no binder component that protrudes from the binder dispersion.

In the composite film according to the fifth embodiment of the present invention, the second transparent conductive film has the structure described above, and therefore compared with a composite film having a simple second transparent conductive film that is formed by applying and then baking a composition containing both conductive oxide microparticles and a binder component, the fill factor, which is one of the factors that determines the conversion efficiency when producing a solar cell, tends to increase. The reason for specifying that the second layer 514 b is 1 to 30% of the volume of the first layer 514 a is because a value within this range yields favorable adhesion and a high fill factor. If this value is less than the lower limit of the above range, then the fill factor tends to decrease, whereas if the value exceeds the upper limit of the range, then the adhesion tends to deteriorate.

The thickness of the second transparent conductive film 514 is within a range from 0.01 to 0.5 μm, and the thickness of the conductive reflective film 515 is within a range from 0.05 to 2.0 μm. If the thickness of the second transparent conductive film is less than the lower limit of the above range, then the short-circuit current of the solar cell decreases, whereas if the thickness exceeds the upper limit of the above range, then the fill factor deteriorates dramatically. The thickness of the second transparent conductive film is preferably within a range from 0.05 to 0.1 μm. If the thickness of the conductive reflective film is less than the lower limit of the above range, then the short-circuit current of the solar cell decreases, whereas if the thickness exceeds the upper limit of the above range, then the amount of material used is more than is necessary, resulting in unnecessary material waste.

Furthermore, the conductive reflective film 515 is formed by using a wet coating method to apply a conductive reflective film composition containing metal nanoparticles to the second transparent conductive film 514. Accordingly, the formed conductive reflective film exhibits favorable film formability and has a high diffuse reflectance. When a film is formed on a substrate of glass or the like, favorable film formability and a high diffuse reflectance can be achieved even when film formation is conducted using a vacuum deposition method such as a sputtering method, but if a vacuum deposition method such as sputtering is used to form a film on top of a second transparent conductive film that has been formed using a wet coating method, then the residual solvent within the second transparent conductive film tends to exert adverse effects on the formed conductive reflective film, meaning forming a conductive reflective film with a high reflectance is difficult.

In this manner, the composite film according to the fifth embodiment of the present invention yields a very high reflectance, due to an improved reflection effect, in terms of optical design, imparted by the second transparent conductive film of low refractive index formed using a wet coating method, as well as favorable film formability and high diffuse reflectance provided by the conductive reflective film.

Moreover, the average diameter of holes occurring at the contact surface of the conductive reflective film 515 on the side of the photovoltaic layer 513 is not more than 100 nm, the average depth at which the holes are positioned is not more than 100 nm, and the number density of the holes is not more than 30 holes/μm². When a transparent substrate having a transmittance of at least 98% is used, a conductive reflective film is obtained for which a high diffuse reflectance equivalent to not less than 80% of the theoretical reflectance can be achieved within a wavelength range from 500 to 1,200 nm. This wavelength range from 500 to 1,200 nm encompasses substantially all convertible wavelengths in those cases where a polycrystalline silicon is used for the photovoltaic layer. The reason for specifying an average diameter for the holes of not more than 100 nm is that, generally, a reflectance spectrum exhibits high reflectance at the long wavelength side of the spectrum and lower reflectance at the short wavelength side, and if the average diameter of the holes exceeds 100 nm, then the inflexion point at which the reflectance starts to decrease tends to shift to a longer wavelength, meaning a favorable reflectance may become unobtainable. Furthermore, the reason for specifying an average depth for the holes of not more than 100 nm is that if the average depth of the holes exceeds 100 nm, then the gradient (slope) of the reflectance spectrum tends to increase, meaning a favorable reflectance may be unobtainable. The reason for specifying a number density for the holes of not more than 30 holes/μm² is that if the number density of the holes exceeds 30 holes/μm², then the reflectance at the long wavelength side of the spectrum tends to decrease, meaning a favorable reflectance may be unobtainable.

The average diameter of the holes is preferably within a range from 5 to 100 nm, the average depth at which the holes are positioned is preferably within a range from 5 to 100 nm, and the number density of the holes is preferably within a range from 2 to 30 holes/μm². If the values for the average diameter of the holes, the average depth at which the holes are positioned, and the number density of the holes are less than the lower limits of the above ranges, then during sintering, the elimination of gas generated by decomposition of the organic molecules of the protective agent used to chemically modify the silver nanoparticles may be inadequate, and as a result, there is a possibility that the remaining organic molecule residues may cause reductions in the conductivity and the reflectance of the conductive reflective film.

Furthermore, the conductive reflective film that constitutes part of the composite film contains one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and this facilitates the setting of the average diameter of holes occurring at the contact surface of the conductive reflective film on the side of the second transparent conductive film to not more than 100 nm, the average depth to not more than 100 nm, and the number density to not more than 30 holes/μm². Furthermore, in the conductive reflective film that constitutes part of the composite film, because the proportion of silver among the metal elements contained within the film is 75% by mass or more, a high reflectance can be achieved. If this proportion is less than 75%, then the reflectance of the conductive reflective film formed using the composition tends to decrease. Furthermore, because the thickness of the conductive reflective film that constitutes part of the composite film is within a range from 0.05 to 2.0 μm, an electrode surface resistance value of the level required of a solar cell can be obtained. Moreover, of the metal nanoparticles incorporated within the conductive reflective film that constitutes part of the composite film, because particles having a particle size within a range from 10 to 50 nm represent a number average of not less than 70%, favorable conductivity and a high reflectance are obtained.

During the formation of the second transparent conductive film, conductive oxide microparticles such as tin oxide powders of ITO (Indium Tin Oxide) and ATO (Antimony Tin Oxide: antimony-doped tin oxide), and zinc oxide powders containing one or more elements selected from the group consisting of Al, Co, Fe, In, Sn and Ti can be used favorably, and of these, ITO, ATO, AZO (Aluminum Zinc Oxide: aluminum-doped zinc oxide), IZO (Indium Zinc Oxide: indium-doped zinc oxide) and TZO (Tin Zinc Oxide: tin-doped zinc oxide) are particularly desirable. In terms of ensuring satisfactory conductivity and favorable film formability, the average particle size of the conductive oxide microparticles is preferably within a range from 2 to 100 nm, and more preferably from 5 to 50 nm.

The coating of the conductive oxide microparticles is formed by preparing a dispersion containing the conductive oxide microparticles dispersed within a dispersion medium, and then using a wet coating method to apply this dispersion. Examples of the dispersion medium include not only water, but also alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone, methyl ethyl ketone, cyclohexanone and isophorone, hydrocarbons such as toluene, xylene, hexane and cyclohexane, amides such as N,N-dimethylformamide and N,N-dimethylacetamide, sulfoxides such as dimethylsulfoxide, glycols such as ethylene glycol, and glycol ethers such as ethyl cellosolve. In order to obtain favorable film formability, the proportion of the dispersion medium within the dispersion is preferably within a range from 50 to 99.99% by mass. The proportion of the conductive oxide microparticles within the dispersion is preferably within a range from 0.01 to 50% by mass. The reason for specifying a proportion of conductive oxide microparticles that satisfies the above range is because at proportions less than the lower limit of the above range, forming a uniform film becomes difficult, whereas if the proportion exceeds the above upper limit, forming a second transparent conductive film having a thickness of not more than 500 nm becomes problematic.

A coupling agent is preferably added to the dispersion of the conductive oxide microparticles depending on the other components used. This coupling agent has the functions of improving the bonding between the conductive microparticles and the binder, and improving the adhesion between the second transparent conductive film and the photovoltaic layer or the conductive reflective film. Examples of the coupling agent include silane coupling agents, aluminum coupling agents and titanium coupling agents.

Examples of the silane coupling agents include vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. Examples of the aluminum coupling agents include the aluminum coupling agent containing acetoalkoxy groups illustrated below in formula (21). Furthermore, examples of the titanium coupling agents include the titanium coupling agents having dialkyl pyrophosphite groups illustrated below in formulas (22) to (24), and the titanium coupling agent having a dialkyl phosphite group illustrated below in formula (25).

The binder dispersion includes, as a binder component, either one or both of a polymeric binder and a non-polymeric binder that cure upon heating. Examples of the polymeric binder include acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, celluloses and siloxane polymers. Furthermore, the polymeric binder preferably includes one or more metal soaps, metal complexes or metal alkoxide hydrolysates of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum or tin. Examples of the non-polymeric binder include metal soaps, metal complexes, metal alkoxides, halosilanes, 2-alkoxyethanols, β-diketones and alkyl acetates. Further, the metal contained within the metal soap, metal complex or metal alkoxide is typically aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium or antimony. These polymeric binders and non-polymeric binders cure upon heating, making it possible to form a second transparent conductive film having a low haze and low volume resistivity at low temperature. The amount of these binders within the binder dispersion is preferably within a range from 0.01 to 50% by mass, and is more preferably within a range from 0.5 to 20% by mass.

During preparation of the binder dispersion, it is preferable to use the same dispersion medium as that used in preparing the dispersion used for forming the conductive oxide microparticles layer. In order to ensure formation of a uniform film, the amount of the dispersion medium is preferably within a range from 50 to 99.99% by mass.

Furthermore, depending on the components used, the addition of a resistance reducer or a water-soluble cellulose derivative or the like may also be preferable. The resistance reducer is preferably one or more materials selected from the group consisting of mineral acid salts and organic acid salts of cobalt, iron, indium, nickel, lead, tin, titanium and zinc. Specific examples include a mixture of nickel acetate and ferric chloride, a mixture of zinc naphthenate, tin octylate and antimony chloride, a mixture of indium nitrate and lead acetate, and a mixture of titanium acetylacetate and cobalt octylate. The amount of these resistance reducers is preferably 0.1 to 10% by mass. Addition of a water-soluble cellulose derivative improves the transparency of the formed second transparent conductive film. Specific examples of the water-soluble cellulose derivative include hydroxypropylcellulose and hydroxypropylmethylcellulose. The amount added of the water-soluble cellulose derivative is preferably within a range from 0.1 to 10% by mass.

The conductive reflective film composition used in forming the conductive reflective film of the fifth embodiment of the present invention is a composition composed of metal nanoparticles dispersed within a dispersion medium. The metal nanoparticles typically include at least 75% by mass, and preferably 80% by mass or more of silver nanoparticles. The reason for specifying an amount of silver nanoparticles of at least 75% by mass relative to 100% by mass of all the metal nanoparticles is because at an amount less than 75% by mass, the reflectance of the conductive reflective film formed using this composition tends to decrease. Furthermore, the silver nanoparticles are chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 1 to 3 carbon atoms.

The reason for restricting the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the metal nanoparticles to a number within a range from 1 to 3 is because if the number of carbon atoms is 4 or greater, then the protective agent becomes difficult to eliminate or decompose (detach and combust) under the heat used during the baking process, meaning a large amount of organic residue tends to remain within the film, which subsequently degenerates or degrades, causing reductions in the conductivity and reflectance of the conductive reflective film.

The silver nanoparticles include a number average of not less than 70%, and preferably not less than 75%, of silver nanoparticles having a primary particle size within a range from 10 to 50 nm. The reason for ensuring that the amount of metal nanoparticles having a primary particle size within a range from 10 to 50 nm is a number average of not less than 70% relative to 100% of all the metal nanoparticles is because if this number average is less than 70%, then the specific surface area of the metal nanoparticles increases and the proportion of the particles composed of organic matter increases, meaning that even if the organic molecules are readily eliminated or decomposed (detached and combusted) under the heat used during baking, because the amount of organic molecules is large, a large amount of organic residue tends to remain within the film, and this residue may subsequently degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film, or the particle size distribution of the metal nanoparticles may broaden considerably, making the density of the conductive reflective film prone to a reduction that causes a deterioration in the conductivity and reflectance of the conductive reflective film. Moreover, another reason for specifying a primary particle size for the metal nanoparticles of 10 to 50 nm is that statistical analyses reveal that metal nanoparticles having a primary particle size within a range from 10 to 50 nm correlate with improved stability over time.

The metal nanoparticles other than the silver nanoparticles are metal nanoparticles formed from one metal, or a mixed composition or alloy composition containing two or more metals, selected from the group consisting of gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese, and the amount of these metal nanoparticles other than the silver nanoparticles, relative to 100% by mass of all the metal nanoparticles, is at least 0.02% by mass but less than 25% by mass, and preferably within a range from 0.03 to 20% by mass. The reason for restricting the amount of the metal nanoparticles other than silver nanoparticles to at least 0.02% by mass but less than 25% by mass relative to 100% by mass of all the metal nanoparticles is because if the amount is less than 0.02% by mass, then although no particular problems arise, amounts within the range from 0.02 to 25% by mass still produce results for the conductivity and reflectance of the conductive reflective film following a weather resistance test (a test that involves standing for 1,000 hours in a constant temperature and humidity chamber at a temperature of 100° C. and a humidity of 50%) that display no deterioration from the results prior to the weather resistance test, whereas on the other hand, if the amount is 25% by mass or greater, then the conductivity and reflectance of the conductive reflective film immediately following baking tend to decrease, and the conductivity and reflectance of the conductive reflective film following a weather resistance test tend to be inferior to the conductivity and reflectance of the conductive reflective film prior to the weather resistance test.

Furthermore, the conductive reflective film composition includes one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils. A metal oxide, metal hydroxide, organometallic compound or silicone oil incorporated within the composition as an additive improves the adhesion to the second transparent conductive film with no loss of conductivity, either due to chemical bonding or an anchoring effect relative to the second transparent conductive film, or due to an improvement in the wettability between the metal nanoparticles and the second transparent conductive film during the baking step.

If the conductive reflective film is formed using a composition that contains none of the above metal oxides and the like, then the surface roughness of the formed conductive reflective film increases, but in order to optimize the photovoltaic conversion efficiency, specific conditions must be satisfied for the uneven shape of the surface of the conductive reflective film, and simply increasing the surface roughness does not necessarily enable the formation of a conductive reflective film surface having superior photovoltaic conversion efficiency. By appropriate adjustment of the variety and concentration and the like of the metal oxide, as described for the fifth embodiment of the present invention, a surface having a surface roughness that optimizes the photovoltaic conversion efficiency can be formed.

The amount of the additives is typically within a range from 0.1 to 20%, and preferably from 0.2 to 10%, of the mass of the silver nanoparticles within the metal nanoparticles. If the amount of these additives is less than 0.1%, then there is a possibility that holes having a large average diameter may be generated, and the density of the holes may increase. An amount of the additives exceeding 20% tends to exert an adverse effect on the conductivity of the formed conductive reflective film, and may result in a volume resistivity exceeding 2×10⁻⁵ Ω·cm.

As the organic polymer used as an additive, one or more polymers selected from the group consisting of polyvinylpyrrolidone (hereafter also abbreviated as PVP), PVP copolymers and water-soluble celluloses are used. Specific examples of the PVP copolymers include PVP-methacrylate copolymers, PVP-styrene copolymers and PVP-vinyl acetate copolymers. Further, examples of the water-soluble celluloses include cellulose ethers such as hydroxypropylmethylcellulose, methylcellulose and hydroxyethylmethylcellulose.

Examples of the metal oxide used as an additive include oxides or composite oxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony. Specific examples of the composite oxides include ITO, ATO and IZO.

Examples of the metal hydroxide used as an additive include hydroxides containing at least one metal selected from the group consisting of aluminum, silicon, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium and antimony.

Examples of the organometallic compound used as an additive include metal soaps, metal complexes and metal alkoxides of at least one metal selected from the group consisting of silicon, titanium, aluminum, antimony, indium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum and tin. Examples of the metal soaps include chromium acetate, manganese formate, iron citrate, cobalt formate, nickel acetate, silver citrate, copper acetate, copper citrate, tin acetate, zinc acetate, zinc oxalate and molybdenum acetate. Furthermore, examples of the metal complexes include a zinc acetylacetonate complex, chromium acetylacetonate complex and nickel acetylacetonate complex. Examples of the metal alkoxides include titanium isopropoxide, methyl silicate, isocyanatopropyltrimethoxysilane and aminopropyltrimethoxysilane.

Examples of the silicone oil used as an additive include both straight silicone oils and modified silicone oils. As the modified silicone oils, oils that include organic groups introduced at a portion of the side chains of a polysiloxane (side-chain type oils), oils that include organic groups introduced at both terminals of a polysiloxane (both terminal-type oils), oils that include an organic group introduced at one of the two terminals of a polysiloxane (single terminal-type oils), and oils that include organic groups introduced at a portion of the side chains and at both terminals of a polysiloxane (side-chain, both terminal-type oils) can be used. Modified silicone oils include both reactive silicone oils and unreactive silicone oils, and a combination of both types may also be used as an additive in the fifth embodiment of the present invention. Reactive silicone oils include amino-modified, epoxy-modified, carboxy-modified, carbinol-modified and mercapto-modified silicone oils, as well as silicone oils modified with a number of different functional groups (such as epoxy groups, amino groups and polyether groups). Unreactive silicone oils include polyether-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, fluorine-modified, and specific hydrophilic-modified silicone oils.

The dispersion medium used in forming the conductive reflective film composition is preferably composed of an alcohol or an alcohol-containing aqueous solution. Examples of alcohols that may be used as the dispersion medium include one or more alcohols selected from the group consisting of methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, diethylene glycol, glycerol, isobornylhexanol and erythritol. The alcohol-containing aqueous solution preferably contains, relative to 100% by mass of the entire dispersion medium, not less than 1% by mass, and preferably 2% by mass or more of water, and not less than 2% by mass, and preferably 3% by mass or more of an alcohol. For example, in those cases where the dispersion medium is composed solely of water and an alcohol, if the medium contains 2% by mass of water, then the alcohol content is 98% by mass, whereas if the medium contains 2% by mass of the alcohol, then the water content is 98% by mass. The reason for specifying a water content of not less than 1% by mass relative to 100% by mass of the entire dispersion medium is because if the water content is less than 1% by mass, then the film obtained by using a wet coating method to apply the conductive reflective film composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate. The reason for specifying an alcohol content of not less than 2% by mass relative to 100% by mass of the entire dispersion medium is because if the alcohol content is less than 2% by mass, then in a similar manner to that described above, the film obtained by using a wet coating method to apply the composition tends to be difficult to sinter at low temperatures, and the conductivity and reflectance of the film following baking tend to deteriorate.

Moreover, the dispersion medium, namely the protective molecules that chemically modify the surface of the metal nanoparticles, preferably contains one or both of a hydroxyl group (—OH) and a carbonyl group (—C═O). If a hydroxyl group (—OH) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action. If a carbonyl group (—C═O) is incorporated within the protective agent that chemically modifies the metal nanoparticles such as the silver nanoparticles, then in a similar manner to that described above, the composition exhibits excellent dispersion stability, and even low-temperature sintering of the coating yields an effective action.

Examples of the method used for producing the conductive reflective film composition include the methods outlined below.

(a) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 3

Firstly, silver nitrate is dissolved in water such as deionized water to prepare a metal salt aqueous solution. In a separate preparation, sodium citrate is dissolved in water such as deionized water to prepare an aqueous solution of sodium citrate having a concentration of 10 to 40%, and ferrous sulfate in a particulate or powder form is then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of an inert gas such as nitrogen gas, thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions. Subsequently, with the reducing agent aqueous solution undergoing constant stirring under a stream of the above inert gas, the metal salt aqueous solution described above is added dropwise to the reducing agent aqueous solution and mixed thoroughly. During this process, it is preferable that the concentrations of the solutions are altered so that the amount added of the metal salt aqueous solution is not more than 1/10th of the amount of the reducing agent aqueous solution, as this ensures that the reaction temperature can be maintained within a range from 30 to 60° C. even if the added metal salt aqueous solution is at room temperature. Further, the mixing ratio between the two aqueous solutions is preferably adjusted so that the equivalent amount of ferrous ions added as the reducing agent is three times the equivalent amount of the metal ions, in other words, (number of mols of metal ions within the metal salt aqueous solution)×(valency of metal ions)=3×(ferrous ions within the reducing agent aqueous solution). Following completion of the dropwise addition of the metal salt aqueous solution, stirring of the resulting mixed liquid is continued for a further 10 to 300 minutes, thus forming a dispersion composed of a metal colloid. This dispersion is left to stand at room temperature, the precipitated metal nanoparticle aggregates are isolated by decantation and/or centrifugal separation and the like, water such as deionized water is added to the isolated nanoparticle aggregates to form a dispersion, a demineralization treatment is conducted using ultrafiltration, and displacement washing is then performed using an alcohol, so as to achieve a metal (silver) content within a range from 2.5 to 50% by mass. Subsequently, by separating the very coarse particles using a centrifugal separator with appropriate adjustment of the centrifugal power, silver nanoparticles are prepared in which those particles having a primary particle size within a range from 10 to 50 nm represent a number average of not less than 70%. In other words, the silver nanoparticles are prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm represents a number average of not less than 70%. By using this method, a dispersion is obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent chemically modifying the silver nanoparticles is 3.

Subsequently, the resulting dispersion is adjusted so that the final metal content (silver content) relative to 100% by mass of the dispersion is within a range from 2.5 to 95% by mass. Further, in those cases where the dispersion medium is an alcohol-containing aqueous solution, the amounts of the water and the alcohol within the medium are preferably adjusted to amounts of not less than 1% and not less than 2% respectively. Furthermore, in those cases where further additives are included within the composition, one or more additives selected from the group consisting of organic polymers, metal oxides, metal hydroxides, organometallic compounds and silicone oils are added in the desired proportions. The amount of these additives is adjusted so as to satisfy a range from 0.1 to 20% by mass relative to 100% by mass of the obtained composition. This enables a composition to be obtained in which silver nanoparticles, which have been chemically modified with a protective agent having an organic molecular main chain in which the number of carbon atoms within the carbon skeleton is 3, are dispersed within the dispersion medium.

(b) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 2

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium malate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 2.

(c) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying the silver nanoparticles is set to 1

With the exception of replacing the sodium citrate used when preparing the reducing agent aqueous solution with sodium glycolate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain that chemically modifies the silver nanoparticles is 1.

(d) The case where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to 3

Examples of the metal that constitutes the metal nanoparticles other than silver nanoparticles include gold, platinum, palladium, ruthenium, nickel, copper, tin, indium, zinc, iron, chromium and manganese. With the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with chlorauric acid, chloroplatinic acid, palladium nitrate, ruthenium trichloride, nickel chloride, cuprous nitrate, tin dichloride, indium nitrate, zinc chloride, iron sulfate, chromium sulfate or manganese sulfate, a dispersion is prepared in the same manner as (a) above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is 3.

In those cases where the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent used for chemically modifying metal nanoparticles other than silver nanoparticles is set to either 1 or 2, a dispersion is prepared in the same manner as either (b) or (c) above, with the exception of replacing the silver nitrate used when preparing the metal salt aqueous solution with one of the other metal salts listed above. This enables a dispersion to be obtained in which the number of carbon atoms within the carbon skeleton of the organic molecular main chain of the protective agent that chemically modifies the metal nanoparticles other than silver nanoparticles is either 1 or 2.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles are combined as the metal nanoparticles, then for example, if the dispersion containing silver nanoparticles produced using the above method (a) is deemed the first dispersion, and the dispersion containing metal nanoparticles other than silver nanoparticles produced using the above method (d) is deemed the second dispersion, a dispersion may be prepared by mixing at least 75% by mass of the first dispersion and less than 25% by mass of the second dispersion so that the combination of the first and second dispersions totals 100% by mass. The first dispersion is not restricted to a dispersion containing silver nanoparticles produced using the above method (a), and a dispersion containing silver nanoparticles produced using the above method (b) or a dispersion containing silver nanoparticles produced using the above method (c) may also be used.

Next is a description of a method for producing a composite film according to the fifth embodiment of the present invention.

In the production process according to the fifth embodiment of the present invention, as illustrated in FIG. 8, a conductive oxide microparticles coating 524 a is first formed by using a wet coating method to apply the aforementioned dispersion, prepared by dispersing conductive oxide microparticles in a dispersion medium, to a photovoltaic layer 513 of a superstrate solar cell that has been laminated on a substrate 511 with a first transparent conductive film 512 disposed therebetween. This application is conducted so that the thickness following baking is within a range from 0.01 to 0.5 μm, and preferably from 0.05 to 0.1 μm. This coating 524 a is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes.

Subsequently, the conductive oxide microparticles coating 524 a is impregnated with the aforementioned binder dispersion 524 b using a wet coating method. The binder dispersion 524 b is caused to penetrate completely into the conductive oxide microparticles coating 524 a to a predetermined depth, so that of the second transparent conductive film formed following baking, the second layer containing no binder component protrudes from the first layer in an amount equivalent to 1 to 30% of the volume of the first layer. The application is preferably conducted so that the mass of the binder component within the applied binder dispersion, relative to the total mass of microparticles contained within the applied conductive oxide microparticles coating, is a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) within a range from 0.05 to 0.5. If the mass ratio is less than the lower limit of the above range, then obtaining satisfactory adhesion is difficult, whereas if the mass ratio exceeds the upper limit of the range, then the surface resistance is likely to increase. The transparent conductive coating 524 formed from the conductive oxide microparticles coating 524 a impregnated with the binder dispersion 524 b is dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes.

Next, a wet coating method is used to apply the above conductive reflective film composition to the transparent conductive coating 524. This application is conducted so that the thickness following baking is within a range from 0.05 to 2.0 μm, and preferably from 0.1 to 1.5 μm. The applied coating is then dried at a temperature of 20 to 120° C., and preferably 25 to 60° C., for a period of 1 to 30 minutes, and preferably 2 to 10 minutes. This completes the formation of the conductive reflective coating 525.

Moreover, the wet coating method mentioned above is preferably one of a spray coating method, dispenser coating method, spin coating method, knife coating method, slit coating method, inkjet coating method, screen printing method, offset printing method or die coating method, although this list is not exhaustive, and any appropriate method may be used.

Spray coating is a method in which either the dispersion is converted to a fine mist using compressed air and then applied to the substrate, or the dispersion itself is pressurized and converted to a fine mist that is then applied to the substrate. Dispenser coating is a method in which, for example, the dispersion is placed inside an injector, and the dispersion is then discharged from a fine nozzle at the tip of the injector and applied to the substrate by depressing the injector piston. Spin coating is a method in which the dispersion is dripped onto a spinning substrate, and the dripped dispersion spreads out to the peripheral edges of the substrate under centrifugal force. Knife coating is a method in which a substrate that is separated from the tip of a knife by a predetermined gap is provided in a manner that enables the substrate to be moved horizontally, and the dispersion is supplied onto the substrate at a point upstream from the knife while the substrate is moved horizontally in the downstream direction. Slit coating is a method in which the dispersion is exuded from a narrow slit and coated onto the substrate. Inkjet coating is a method in which the dispersion is used to fill the ink cartridge of a commercially available inkjet printer, and the dispersion is then applied to the substrate by inkjet printing. Screen printing is a method in which a gauze is used as a patterning material, and the dispersion is transferred to the substrate through a print image formed on the gauze. Offset printing is a printing method that utilizes the water repellency of ink, wherein the dispersion applied to a plate is not adhered directly to the substrate, but is rather first transferred from the plate to a rubber sheet, before being subsequently transferred from the rubber sheet to the substrate. Die coating is a method in which a dispersion that has been supplied to a die is distributed using a manifold, and is then extruded in a thin film from a slit, and applied to the surface of a moving substrate. Die coating methods include slot coating, slide coating and curtain coating methods.

Finally, the substrate 511 having the coating 526 formed thereon is subjected to baking, either under normal atmospheric conditions or in an inert gas atmosphere of nitrogen or argon or the like, by holding the substrate at a temperature of 130 to 400° C., and preferably 150 to 350° C., for a period of 5 to 60 minutes, and preferably 15 to 40 minutes. The reason for conducting the application of the conductive oxide microparticles dispersion so that the thickness of the second transparent conductive film following baking is within a range from 0.01 to 0.5 μm is because if the thickness following baking is less than 0.01 μm, then the short-circuit current of the solar cell decreases, whereas if the thickness exceeds 0.5 μm, then the fill factor deteriorates dramatically. Furthermore, the reason for conducting the application of the conductive reflective film composition so that the thickness of the conductive reflective film following baking is within a range from 0.05 to 2.0 μm is because if the thickness is less than 0.05 μm, then the surface resistance value becomes overly high, making it difficult to obtain the level of conductivity required of a solar cell electrode, whereas if the thickness exceeds 2.0 μm, then although there are no concerns in terms of the resulting properties, the amount of material used is more than is necessary, resulting in unnecessary material waste.

The reason for specifying a baking temperature within a range from 130 to 400° C. is because at temperatures lower than 130° C., a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. In contrast, if the temperature exceeds 400° C., then any merit associated with conducting the production using a low-temperature process is lost. In other words, the production costs increase, and the productivity tends to decrease. Furthermore, amorphous silicon solar cells, microcrystalline silicon solar cells, and hybrid silicon solar cells that use both these forms of silicon are particularly susceptible to heat, and a high temperature during the baking step causes a deterioration in the conversion efficiency.

The reason for specifying a baking time within a range from 5 to 60 minutes for the substrate having the coating formed thereon is because if the baking time is less than the lower limit of this range, then a problem arises in that the surface resistance value of the second transparent conductive film in the composite film tends to become overly high. Further, sintering of the metal nanoparticles within the conductive reflective film tends to be inadequate, and elimination or decomposition (detachment and combustion) of the protective agent under the heat used during baking becomes difficult, meaning a large amount of organic residue tends to be retained within the conductive reflective film following baking. This residue tends to degenerate or degrade, causing reductions in the conductivity and reflectance of the conductive reflective film. Although lengthening the baking time beyond the upper limit of the above range has no adverse effects on the composite film properties, it results in an unnecessary increase in production costs and decrease in productivity. Moreover, the conversion efficiency of the solar cell also tends to deteriorate.

The composite film of the fifth embodiment of the present invention can be formed in the manner described above. In this manner, by using a wet coating method, the production process according to the fifth embodiment of the present invention is able to eliminate vacuum processes such as vacuum deposition and sputtering as far as possible, meaning the composite film can be produced comparatively cheaply.

In the first through fifth embodiments, there are no particular restrictions on the first transparent conductive film, and examples of films that may be used include films formed using the same formation method as that employed for the second transparent conductive film, and films formed using a vacuum deposition method such as sputtering.

EXAMPLES

A detailed description of examples and comparative examples is presented below.

Examples A1 to A32

Transparent conductive film compositions for composite films according to the first embodiment of the present invention were prepared using the components and amounts listed for the classifications A1 to A8 detailed below in Table 1. The classification numbers from Table 1 for the transparent conductive film compositions used within the various examples are listed in Table 2 and Table 3.

In classification A1, as detailed below in Table 1, a total of 60 g of a mixture composed of 15% by mass of an IZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 72.77% by mass of isopropanol as a dispersion medium, 10% by mass of a mixed liquid of the non-polymeric binders 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione as a binder, and 2.23% by mass of a mixture of indium nitrate and lead acetate (mass ratio 1:1) as a resistance reducer was placed in a 100 cc glass bottle, and using 100 g of zirconia beads with a diameter of 0.3 mm (MICRO HICA, manufactured by Showa Shell Sekiyu K.K.), the mixture was dispersed for 6 hours using a paint shaker, thus yielding a transparent conductive film composition.

In classification A2, as detailed below in Table 1, a transparent conductive film composition was prepared in the same manner as the classification A1, using a mixture composed of 7.5% by mass of an ITO powder having an average particle size of 0.025 μm as a conductive oxide powder, 92.3% by mass of a first mixed liquid composed of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1) as a dispersion medium, 0.038% by mass of the non-polymeric binder 2,4-pentanedione as a binder, and 0.162% by mass of a titanium coupling agent represented by the above formula (4) as a coupling agent.

In classification A3, as detailed below in Table 1, a transparent conductive film composition was prepared in the same manner as the classification A1, using a mixture composed of 5% by mass of an ATO powder having an average particle size of 0.025 μm as a conductive oxide powder, 50.99% by mass of the above first mixed liquid as a dispersion medium, 44% by mass of the non-polymeric binder 2-n-propoxyethanol as a binder, and 0.01% by mass of a titanium coupling agent represented by the above formula (4) as a coupling agent.

In classification A4, as detailed below in Table 1, a transparent conductive film composition was prepared in the same manner as the classification A1, using a mixture composed of 5% by mass of an AZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 74.64% by mass of the above first mixed liquid as a dispersion medium, 20% by mass of a mixed liquid of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1) as a binder, and 0.36% by mass of a titanium coupling agent represented by the above formula (3) as a coupling agent.

In classification A5, as detailed below in Table 1, a transparent conductive film composition was prepared in the same manner as the classification A1, using a mixture composed of 5% by mass of a TZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 93.95% by mass of the above first mixed liquid as a dispersion medium, 0.8% by mass of a mixed liquid of 2-isobutoxyethanol, 2-hexyloxyethanol and n-propyl acetate (mass ratio 4:1:1) as a binder, and 0.25% by mass of a titanium coupling agent represented by the above formula (5) as a coupling agent.

In classification A6, first, an ATO powder having an average particle size of 0.010 μm was suspended in water, the pH of the suspension was adjusted to a value of 7, and the suspension was treated for 30 minutes using a beads mill. Subsequently, hydroxypropylcellulose was added to the suspension as a water-soluble cellulose derivative in a mass ratio of 0.01% relative to the mass of the ATO powder, thus forming a conductive water dispersion. The conductive water dispersion prepared in this manner was adjusted to a solid fraction concentration of 18.5%, and 100 g of this dispersion and 100 g of a 13.2% by mass aqueous solution of gelatin were mixed at 40° C., thus forming a water-based transparent conductive film composition.

In classification A7, as detailed below in Table 1, a transparent conductive film composition was prepared by mixing 5.3% by mass of an ATO powder having an average particle size of 0.025 μm as a conductive oxide powder, 85% by mass of a second mixed liquid composed of ethanol and butanol (mass ratio 98:2) as a dispersion medium, 1.7% by mass of a SiO₂ binding agent as a binder, and 8.0% by mass of a titanium coupling agent represented by the above formula (3) as a coupling agent. The SiO₂ binding agent used as a binder was prepared using a 500 ml four-neck glass flask, by charging the flask with 140 g of tetraethoxysilane and 240 g of ethyl alcohol, adding 1.0 g of 12N-HCl dissolved in 25 g of pure water in a single batch with constant stirring, and then reacting the resulting mixture for 6 hours at 80° C.

In classification A8, as detailed below in Table 1, a transparent conductive film composition was prepared by mixing 8.0% by mass of an ITO powder having an average particle size of 0.025 μm as a conductive oxide powder, 88% by mass of the above second mixed liquid as a dispersion medium, 2.0% by mass of a SiO₂ binding agent as a binder, and 2.0% by mass of a titanium coupling agent represented by the above formula (2) as a coupling agent. The SiO₂ binding agent used as a binder was prepared in the same manner as that described for classification A7.

Next, using the procedure described below, conductive reflective film compositions for composite films according to the first embodiment of the present invention were prepared.

First, silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution. Further, in a separate preparation, sodium citrate was dissolved in deionized water to prepare an aqueous solution of sodium citrate having a concentration of 26% by mass. A particulate ferrous sulfate was then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of nitrogen gas held at a temperature of 35° C., thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions.

Subsequently, with the stream of nitrogen gas held at 35° C., a magnetic stirrer bar was placed in the reducing agent aqueous solution, and with the reducing agent aqueous solution undergoing constant stirring by rotating the stirrer bar at a rate of 100 rpm, the metal salt aqueous solution was added dropwise to the reducing agent aqueous solution and mixed thoroughly. For this addition, the concentration of each of the solutions was altered so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution was not more than 1/10th of the amount of the reducing agent aqueous solution, thereby ensuring that the reaction temperature was maintained at 40° C. even though the added metal salt aqueous solution was at room temperature. Furthermore, the mixing ratio between the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the molar ratios of both the citrate ions and the ferrous ions within the reducing agent aqueous solution, relative to the total atomic valence number of metal ions within the metal salt aqueous solution, was a 3-fold molar excess. Following completion of the dropwise addition of the metal salt aqueous solution to the reducing agent aqueous solution, stirring of the resulting mixed liquid was continued for a further 15 minutes, thereby generating metal particles within the mixed liquid and forming a metal particles dispersion containing dispersed metal particles. The pH of the metal particles dispersion was 5.5, and the stoichiometric amount of generated metal particles within the dispersion was 5 Oita.

The thus obtained dispersion was left to stand at room temperature to allow the metal particles within the dispersion to settle out, and the settled metal particle aggregates were isolated by decantation. Deionized water was added to the isolated metal aggregates to form a dispersion, a demineralization treatment was conducted using ultrafiltration, and displacement washing was then performed using methanol, so as to achieve a metal (silver) content of 50% by mass. Subsequently, by using a centrifugal separator with appropriate adjustment of the centrifugal power to separate the comparatively large silver particles having a particle size exceeding 100 nm, a sample was prepared in which silver particles having a primary particle size within a range from 10 to 50 nm represented a number average of 71%. In other words, the silver nanoparticles were prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm was a number average of 71%. The thus obtained silver nanoparticles were chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 3 carbon atoms.

Next, 10 parts by mass of the obtained metal nanoparticles were added to and dispersed within 90 parts by mass of a mixed solution of ethanol and methanol, and by subsequently adding the additives listed below in Table 2 to Table 4 in the proportions shown in Table 2 to Table 4, a series of conductive reflective film compositions was obtained. The metal nanoparticles used in forming these conductive reflective film compositions contained at least 75% of silver nanoparticles.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles were combined as the metal nanoparticles, then the dispersion containing silver nanoparticles produced using the above method was deemed the first dispersion, a dispersion containing metal nanoparticles other than silver nanoparticles was prepared using the same method as the above method used for producing the silver nanoparticles, but with the exception of replacing the silver nitrate with a metal salt listed in Table 2 to Table 4 that is capable of forming metal nanoparticles other than silver nanoparticles, and this dispersion of metal nanoparticles was deemed the second dispersion, and the first dispersion and second dispersion were then mixed together, prior to the addition of additives, in the proportions listed in Table 2 to Table 4, thus forming a conductive reflective film composition.

Each of the prepared transparent conductive film compositions was applied to the substrate listed in Table 2 to Table 4 using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.7 to 1.3×10² nm, and was then dried at a temperature of 25° C. for 5 minutes to form a transparent conductive coating. Subsequently, one of the prepared conductive reflective film compositions was applied to the formed transparent conductive coating using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 10² to 2×10³ nm, and was then dried at a temperature of 25° C. for 5 minutes to form a conductive reflective coating. By subsequently performing baking under the conditions detailed in Table 2 to Table 4, a composite film was formed on the substrate.

In Table 2 to Table 4, PVP represents a polyvinylpyrrolidone having a Mw of 360,000, and PET represents a polyethylene terephthalate.

Comparative Example A1

A second transparent conductive film was formed with a thickness of 0.7×10² nm using a sputtering method that represents an example of a vacuum deposition method, and a conductive reflective film was then formed on top of this second transparent conductive film, using the same conductive reflective film composition as that used in example A1 and the same method as that used in example A1, thus forming a composite film.

Comparative Example A2

A second transparent conductive film was formed with a thickness of 2.0×10² nm using a sputtering method that represents an example of a vacuum deposition method, and a conductive reflective film was then formed on top of this second transparent conductive film, using the same conductive reflective film composition as that used in example A1 and the same method as that used in example A1, thus forming a composite film.

TABLE 1 Transparent conductive film composition Classifi- Conductive oxide cation microparticles Dispersion medium Binder Coupling agent Other A1 IZO Isopropanol Non-polymeric binder None Resistance reducer 15% by mass 72.77% by mass 10% by mass 2.23% by mass A2 ITO First mixed liquid Non-polymeric binder Titanium coupling agent None 7.5% by mass 92.3% by mass 0.038% by mass 0.162% by mass A3 ATO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 50.99% by mass 44% by mass 0.01% by mass A4 AZO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 74.64% by mass 20% by mass 0.36% by mass A5 TZO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 93.95% by mass 0.8% by mass 0.25% by mass A6 ATO Water Gelatin None Water-soluble cellulose 9.249% by mass 84.150% by mass 6.600% by mass derivative 0.001% by mass A7 ATO Second mixed liquid SiO₂ binding agent Titanium coupling agent None 5.3% by mass 85% by mass 1.7% by mass 8.0% by mass A8 ITO Second mixed liquid SiO₂ binding agent Titanium coupling agent None 8.0% by mass 88% by mass 2.0% by mass 2.0% by mass

TABLE 2 Transparent Conductive reflective film Coating method Baking treatment conductive film composition Transparent Conductive Temp- composition Metal conductive reflective erature Time Atmo- Classification nanoparticles Additives film film Substrate [° C.] [min.] sphere Example A1 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air A1 Ni acetate 1% by mass Example A2 Ag 96% by mass PVP 3% by mass Spin coating Glass 200 20 air A2 Cu acetate 1% by mass Example A3 Ag 89% by mass PVP-dimethylaminoethyl Spin coating Glass 200 20 air A3 Au 5% by mass methacrylate 5% by mass Zn acetate 1% by mass Example A6 Ag 72% by mass Methylcellulose 3% by mass Spin coating Glass 200 20 air A4 Pd 24% by mass Mo acetate 1% by mass Example A6 Ag 94% by mass Hydroxypropylmethyl- Spin coating Glass 200 20 air A5 Ru 2% by mass cellulose 3% by mass Sn acetate 1% by mass Example A4 Ag 92% by mass PVP 3% by mass Dispenser coating Glass 130 20 N₂ A6 Cu 4% by mass Sn acetate 1% by mass Example A5 Ag 95.8% by mass PVP 3% by mass Dispenser coating Glass 200 20 air A7 Sn 0.2% by mass Sn acetate 1% by mass Example A1 Ag 96.8% by mass PVP 2% by mass Dispenser coating Glass 130 20 air A8 In 0.2% by mass Sn acetate 1% by mass Example A1 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air A9 Zn 0.2% by mass Sn acetate 1% by mass Example A1 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air A10 Fe 0.2% by mass Zn acetate 1% by mass Example A1 Ag 95.8% by mass PVP 3% by mass Screen printing Glass 150 20 air A11 Fe 0.2% by mass Ni acetate 1% by mass Example A1 Ag 96.8% by mass PVP 3% by mass Screen printing Glass 150 20 air A12 Mn 0.2% by mass Example A2 Ag 90% by mass PVP 9% by mass Knife coating Glass 150 60 air A13 Al₂O₃ 1% by mass Example A2 Ag 99% by mass PVP 0.9% by mass Slit coating Glass 400 60 air A14 SiO₂ 0.1% by mass Example A2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air A15 TiO₂ 1% by mass

TABLE 3 Transparent Conductive reflective film Coating method Baking treatment conductive film composition Transparent Conductive Temp- composition Metal conductive reflective erature Time Atmo- Classification nanoparticles Additives film film Substrate [° C.] [min.] sphere Example A2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air A16 Cr₂O₃ 1% by mass Example A2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air A17 MnO₂ 1% by mass Example A2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air A18 Fe₂O₃ 0.5% by mass Cr₃O₄ 0.5% by mass Example A2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air A19 Ag₂O 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 Ar A20 Cu(OH)₂ 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A21 ZnO 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A22 MoO₂ 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A23 SnO₂ 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A24 ITO 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A25 ATO 1% by mass Example A3 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A26 Methyl silicate 1% by mass Example A7 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A27 Titanium isopropoxide 1% by mass Example A7 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A28 Ammonium chromate 1% by mass Example A7 Ag 95.9% by mass PVP 4% by mass Spin coating PET 150 20 air A29 Mn formate 0.1% by mass Example A7 Ag 95-9% by mass PVP 4% by mass Spin coating PET 150 20 air A30 Fe citrate 0.1% by mass

TABLE 4 Transparent Conductive reflective film Coating method Baking treatment conductive film composition Transparent Conductive Temp- composition Metal conductive reflective erature Time Atmo- Classification nanoparticles Additives film film Substrate [° C.] [min.] sphere Example A7 Ag 95.9% by mass PVP 4% by mass Spin coating PET 200 20 air A31 Co formate 0.01% by mass Example A8 Ag 95% by mass Ni acetate Spin coating PET 150 20 air A32 5% by mass Example A8 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air A33 Ag citrate 1% by mass Example A8 Ag 95% by mass Cu acetate Spin coating PET 150 20 N₂ A34 5% by mass Example A8 Ag 95% by mass Zn acetate Spin coating PET 150 20 air A35 5% by mass Example A8 Ag 95% by mass Mn acetate Spin coating PET 150 20 air A36 5% by mass Example A8 Ag 95% by mass Sn acetate Die coating PET 150 20 air A37 5% by mass Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example A1 sputter film Ni acetate 1% by mass coating Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example A2 sputter film Ni acetate 1% by mass coating <Comparative Test A1>

The reflectance and film thickness of the second transparent conductive film within each of the composite films obtained in examples A1 to A37 and comparative examples A1 and A2 were evaluated. The results of the evaluations are listed below in Table 5 and Table 6. First, the thicknesses of the second transparent conductive film and the conductive reflective film following baking were measured directly from a film cross-section obtained using a SEM (scanning electron microscope S800, manufactured by Hitachi, Ltd.).

<Comparative Test A2>

Each of the substrates having a conductive reflective film formed thereon obtained in examples A1 to A37 and comparative examples A1 and A2 was evaluated for the distribution of holes at the substrate-side contact surface of the conductive reflective film, the back side reflectance and the thickness of the conductive reflective film. The results of these evaluations are listed below in Table 5 and Table 6.

Measurement of the holes was conducted using different methods, depending on whether or not the conductive reflective film was able to be pulled away from the second transparent conductive film.

In those examples where the conductive reflective film was able to be pulled away from the substrate, first, an adhesive was applied to a jig having a flat surface, and the jig was pressed against the conductive reflective film bonded to the second transparent conductive film. Following a holding period to allow the adhesive to dry and generate a powerful adhesion, the jig was pulled perpendicularly away from the substrate using a pull tester (EZ-TEST, manufactured by Shimadzu Corporation), thereby pulling the conductive reflective film away from the second transparent conductive film.

Subsequently, the uneven surface of the conductive reflective film exposed on the jig that had been peeled away from the second transparent conductive film, which prior to peeling was the substrate-side contact surface of the conductive reflective film, was inspected using an atomic force microscope (AFM). The uneven surface was analyzed, and the average diameter, average depth and number density of the holes that appeared at the film surface were evaluated. The average diameter was determined by measuring the maximum length and minimum length across each opening, and calculating the average value.

Further, another method of pulling the conductive reflective film away from the second transparent conductive film, in which a double-sided tape was bonded to the conductive reflective film, and one end of this tape was then pulled up, thereby peeling the conductive reflective film away from the second conductive reflective film, was also used.

In those examples where the conductive reflective film was not able to be pulled away from the second transparent conductive film, first the conductive reflective film bonded to the second transparent conductive film was processed using a focused ion beam (FIB) to expose a cross-section of the sample. This sample cross-section was inspected using a scanning electron microscope (SEM), and the shape of the metal film/substrate interface was observed. The diameter, average depth and number density of openings within this interface image were evaluated. For each of the evaluated openings, the diameter was taken as being the maximum length across the opening within the cross-sectional image.

Evaluation of the back side reflectance of the conductive reflective film was performed using a combination of an ultraviolet-visible spectrophotometer and an integrating sphere, by measuring the diffuse reflectance of the conductive reflective film at wavelengths of 500 nm and 1,100 nm.

The film thickness of the conductive reflective film was measured from a cross-sectional image obtained using a scanning electron microscope (SEM).

<Comparative Test A3>

The adhesion to the substrate of each of the composite films obtained in examples A1 to A37 and comparative examples A1 and A2 was evaluated. The results of the evaluations are listed in Table 5 and Table 6. The adhesion was evaluated qualitatively on the basis of a peel test in which an adhesive tape was bonded to, and then peeled from, the composite film formed on the substrate. A result of “good” was recorded in those cases where only the adhesive tape peeled from the substrate, a result of “fair” was recorded in those cases where a mixed state was obtained in which only the adhesive tape peeled in some portions and the substrate surface was exposed in other portions, and a result of “poor” was recorded in those cases where peeling of the adhesive tape exposed the entire substrate surface.

TABLE 5 Composite film Conductive reflective film Hole distribution at substrate-side Transparent contact surface Back side conductive film Average Average Number reflectance Thickness diameter depth density [%] Thickness [nm] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example A1 1.0 × 10² 70 70 20 85 94 1.0 × 10² Good Example A2 1.0 × 10² 80 50 10 84 94 5.0 × 10² Good Example A3 1.0 × 10² 89 50 10 80 91 1.0 × 10³ Good Example A4 1.3 × 10² 70 90 5 82 93 1.1 × 10³ Good Example A5 1.3 × 10² 90 50 10 82 92 1.0 × 10³ Good Example A6 1.0 × 10² 90 70 20 83 94 1.2 × 10³ Good Example A7 1.0 × 10² 80 60 15 84 94 1.0 × 10³ Good Example A8 1.0 × 10² 70 45 22 91 95 1.0 × 10³ Good Example A9 1.0 × 10² 90 70 16 85 94 1.9 × 10³ Good Example A10 1.0 × 10² 80 60 20 84 95 1.8 × 10³ Good Example A11 1.0 × 10² 70 50 20 84 94 2.0 × 10³ Good Example A12 1.0 × 10² 60 90 10 82 93 2.0 × 10³ Good Example A13 1.0 × 10² 50 95 5 87 95 2.0 × 10³ Good Example A14 1.0 × 10² 90 80 20 85 82 1.9 × 10³ Good Example A15 1.0 × 10² 70 60 25 84 94 1.0 × 10³ Good Example A16 1.0 × 10² 80 65 15 80 95 1.1 × 10³ Good Example A17 1.0 × 10² 90 60 20 91 91 1.0 × 10³ Good Example A18 1.0 × 10² 40 50 10 92 92 1.2 × 10³ Good Example A19 1.0 × 10² 30 30 10 94 94 1.2 × 10³ Good Example A20 1.0 × 10² 50 50 10 91 92 1.0 × 10³ Good

TABLE 6 Composite film Conductive reflective film Hole distribution at substrate-side Transparent contact surface Back side conductive film Average Average Number reflectance Thickness diameter depth density [%] Thickness [nm] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example A21 1.0 × 10² 80 80 20 82 88 1.0 × 10³ Good Example A22 1.0 × 10² 90 90 28 81 82 1.0 × 10³ Good Example A23 1.0 × 10² 80 75 25 82 82 1.0 × 10³ Good Example A24 1.0 × 10² 50 90 20 82 85 1.1 × 10³ Good Example A25 1.0 × 10² 70 80 15 83 85 1.0 × 10³ Good Example A26 1.0 × 10² 60 90 20 83 85 1.1 × 10³ Good Example A27 1.0 × 10² 40 50 15 82 84 1.0 × 10³ Good Example A28 0.7 × 10² 95 95 12 80 89 1.1 × 10³ Good Example A29 0.7 × 10² 80 85 5 85 88 1.0 × 10³ Good Example A30 0.7 × 10² 55 80 10 89 90 1.0 × 10³ Good Example A31 0.7 × 10² 50 90 5 88 91 1.2 × 10³ Good Example A32 0.7 × 10² 80 80 10 86 87 1.1 × 10³ Good Example A33 0.7 × 10² 70 60 15 88 88 1.0 × 10³ Good Example A34 0.7 × 10² 90 60 20 85 86 1.0 × 10³ Good Example A35 0.7 × 10² 80 90 10 82 85 1.0 × 10³ Good Example A36 0.7 × 10² 80 70 20 82 89 1.1 × 10³ Good Example A37 0.7 × 10² 90 50 10 84 88 1.0 × 10³ Good Comparative 0.7 × 10² 70 70 20 70 80 1.0 × 10² Good example A1 Comparative 2.0 × 10² 70 70 20 75 90 1.0 × 10³ Fair example A2

As is evident from Table 5 and Table 6, of the comparative examples A1 and A2 in which the second transparent conductive film was formed by a sputtering method that represents a vacuum deposition method, comparative example A2 exhibited inferior adhesion to examples A1 to A37. In comparative example A1, the reflectance at 500 nm was a low value of only 70%, and even at 1,100 nm, the reflectance tended to be low. Furthermore, although the reflectance at 1,100 nm in comparative example A2 was a high value of 90%, the reflectance at 500 nm was a comparatively low value of only 75%, confirming that the reflectance varied considerably depending on the wavelength. In contrast, in examples A1 to A37, high reflectance values of not less than 80% were achieved at both the 500 nm wavelength and the 1,100 nm wavelength.

Examples B1 to B32

Conductive oxide microparticles dispersions and binder dispersions were prepared using the components and amounts listed for the classifications B1 to B8 detailed below in Table 7. The classification numbers from Table 7 for the dispersions used within the various examples are listed in Table 8 and Table 9.

In classification B1, as detailed below in Table 7, a total of 60 g of a mixture composed of 20% by mass of an IZO powder having an average particle size of 0.025 μm as conductive oxide microparticles and 80% by mass of isopropanol as a dispersion medium was placed in a 100 cc glass bottle, and using 100 g of zirconia beads with a diameter of 0.3 mm (MICRO HICA, manufactured by Showa Shell Sekiyu K.K.), the mixture was dispersed for 6 hours using a paint shaker, thus yielding a dispersion of conductive oxide microparticles. Further, in a separate preparation, 10% by mass of a mixed liquid of the non-polymeric binders 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione as the binder, 88.2% by mass of isopropanol as a dispersion medium, and 1.8% by mass of a mixture of indium nitrate and lead acetate (mass ratio 1:1) as a resistance reducer were combined and stirred for one hour at room temperature at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification B2, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using a mixture composed of 7.5% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.2% by mass of a titanium coupling agent represented by the above formula (9) as a coupling agent, and 92.3% by mass of a first mixed liquid composed of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1) as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification B1, using 10% by mass of the non-polymeric binder 2,4-pentanedione as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification B3, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using a mixture composed of 10% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.02% by mass of a titanium coupling agent represented by the above formula (9) as a coupling agent, and 89.98% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification B1, using 10% by mass of the non-polymeric binder 2-n-propoxyethanol as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification B4, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using a mixture composed of 10% by mass of an AZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 1% by mass of a titanium coupling agent represented by the above formula (8) as a coupling agent, and 89% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification B1, using 10% by mass of a mixed liquid of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification B5, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using a mixture composed of 5% by mass of a TZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.5% by mass of a titanium coupling agent represented by the above formula (10) as a coupling agent, and 94.5% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification B1, using 10% by mass of a mixed liquid of 2-isobutoxyethanol, 2-hexyloxyethanol and n-propyl acetate (mass ratio 4:1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification B6, first, an ATO powder having an average particle size of 0.010 μm was suspended in water, the pH of the suspension was adjusted to a value of 7, and the suspension was treated for 30 minutes using a beads mill. The above first mixed liquid was added to the treated suspension as a dispersion medium, and the solid fraction concentration was adjusted to 18.5%, thus yielding a dispersion of conductive oxide microparticles. Further, a mixture containing 5% of gelatin as a binder, 1% by mass of hydroxypropylcellulose as a water-soluble cellulose derivative, and 94% by mass of water as the dispersion medium was stirred for one hour at a temperature of 30° C. at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification B7, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using a mixture composed of 6% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 85% by mass of a second mixed liquid composed of ethanol and butanol (mass ratio 98:2) as a dispersion medium, and 9.0% by mass of a titanium coupling agent represented by the above formula (8) as a coupling agent. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium. The SiO₂ binding agent used as a binder was prepared using a 500 ml four-neck glass flask, by charging the flask with 140 g of tetraethoxysilane and 240 g of ethyl alcohol, adding 1.0 g of 12N-HCl dissolved in 25 g of pure water in a single batch with constant stirring, and then reacting the resulting mixture for 6 hours at 80° C.

In classification B8, as detailed below in Table 7, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification B1, using 8% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 2.0% by mass of a titanium coupling agent represented by the above formula (7) as a coupling agent, and 90% by mass of the above second mixed liquid as a dispersion medium. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium.

Next, using the procedure described below, conductive reflective film compositions were prepared.

First, silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution. Further, in a separate preparation, sodium citrate was dissolved in deionized water to prepare an aqueous solution of sodium citrate having a concentration of 26% by mass. A particulate ferrous sulfate was then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of nitrogen gas held at a temperature of 35° C., thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions.

Subsequently, with the stream of nitrogen gas held at 35° C., a magnetic stirrer bar was placed in the reducing agent aqueous solution, and with the reducing agent aqueous solution undergoing constant stirring by rotating the stirrer bar at a rate of 100 rpm, the metal salt aqueous solution was added dropwise to the reducing agent aqueous solution and mixed thoroughly. For this addition, the concentration of each of the solutions was altered so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution was not more than 1/10th of the amount of the reducing agent aqueous solution, thereby ensuring that the reaction temperature was maintained at 40° C. even though the added metal salt aqueous solution was at room temperature. Furthermore, the mixing ratio between the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the molar ratios of both the citrate ions and the ferrous ions within the reducing agent aqueous solution, relative to the total atomic valence number of metal ions within the metal salt aqueous solution, was a 3-fold molar excess. Following completion of the dropwise addition of the metal salt aqueous solution to the reducing agent aqueous solution, stirring of the resulting mixed liquid was continued for a further 15 minutes, thereby generating metal particles within the mixed liquid and forming a metal particles dispersion containing dispersed metal particles. The pH of the metal particles dispersion was 5.5, and the stoichiometric amount of generated metal particles within the dispersion was 5 g/liter.

The thus obtained dispersion was left to stand at room temperature to allow the metal particles within the dispersion to settle out, and the settled metal particle aggregates were isolated by decantation. Deionized water was added to the isolated metal aggregates to form a dispersion, a demineralization treatment was conducted using ultrafiltration, and displacement washing was then performed using methanol, so as to achieve a metal (silver) content of 50% by mass. Subsequently, by using a centrifugal separator with appropriate adjustment of the centrifugal power to separate the comparatively large silver particles having a particle size exceeding 100 nm, a sample was prepared in which silver particles having a primary particle size within a range from 10 to 50 nm represented a number average of 71%. In other words, the silver nanoparticles were prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm was a number average of 71%. The thus obtained silver nanoparticles were chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 3 carbon atoms.

Next, 10 parts by mass of the obtained metal nanoparticles were added to and dispersed within 90 parts by mass of a mixed solution of ethanol and methanol, and by subsequently adding the additives listed below in Table 8 to Table 10 in the proportions shown in Table 8 to Table 10, a series of conductive reflective film compositions was obtained. The metal nanoparticles used in forming these conductive reflective film compositions contained at least 75% of silver nanoparticles.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles were combined as the metal nanoparticles, then the dispersion containing silver nanoparticles produced using the above method was deemed the first dispersion, a dispersion containing metal nanoparticles other than silver nanoparticles was prepared using the same method as the above method used for producing the silver nanoparticles, but with the exception of replacing the silver nitrate with a metal salt listed in Table 8 to Table 10 that is capable of forming metal nanoparticles other than silver nanoparticles, and this dispersion of metal nanoparticles was deemed the second dispersion, and the first dispersion and second dispersion were then mixed together, prior to the addition of additives, in the proportions listed in Table 8 to Table 10, thus forming a conductive reflective film composition.

Finally, composite films were formed using the conductive oxide microparticles dispersions, binder dispersions and conductive reflective film compositions prepared above. Specifically, one of the prepared dispersions of conductive oxide microparticles was applied to the substrate listed in Table 8 to Table 10 using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.01 to 0.5 μm, and was then dried at a temperature of 25° C. for 5 minutes to form a coating of the conductive oxide microparticles. Next, this coating of conductive oxide microparticles was impregnated with one of the prepared binder dispersions using one of a variety of different coating methods so that, following baking, the entire surface of the conductive oxide microparticles layer was covered with the binder layer, and the binder dispersion was then dried at a temperature of 25° C. for 5 minutes to form a transparent conductive coating. The binder dispersion was applied in such a manner that the mass of the binder component within the binder dispersion, relative to the total mass of microparticles contained within the applied coating of the conductive oxide microparticles was a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) listed in Table 8 to Table 10. Subsequently, one of the prepared conductive reflective film compositions was applied to the transparent conductive coating using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.05 to 2.0 μm, and was then dried at a temperature of 25° C. for 5 minutes to form a conductive reflective coating. By subsequently performing baking under the conditions detailed in Table 8 to Table 10, a composite film was formed on the substrate.

In Table 8 to Table 10, PVP represents a polyvinylpyrrolidone having a Mw of 360,000, and PET represents a polyethylene terephthalate.

Comparative Example B1

A second transparent conductive film was formed with a thickness of 0.7×10² nm using a sputtering method that represents an example of a vacuum deposition method, and a conductive reflective film was then formed on top of this second transparent conductive film, using the same conductive reflective film composition as that used in example B1 and the same method as that used in example B1, thus forming a composite film.

Comparative Example B2

A second transparent conductive film was formed with a thickness of 2.0×10² nm using a sputtering method that represents an example of a vacuum deposition method, and a conductive reflective film was then formed on top of this second transparent conductive film, using the same conductive reflective film composition as that used in example B1 and the same method as that used in example B1, thus forming a composite film.

TABLE 7 Conductive oxide microparticles dispersion Binder dispersion Classifi- Conductive oxide Dispersion cation microparticles Dispersion medium Coupling agent Binder medium Other B1 IZO Isopropanol None Non-polymeric Isopropanol Resistance reducer 20% by mass 80% by mass binder 88.2% by mass 1.8% by mass 10% by mass B2 ITO First mixed liquid Titanium coupling Non-polymeric First mixed liquid None 7.5% by mass 92.3% by mass agent binder 90% by mass 0.2% by mass 10% by mass B3 ATO First mixed liquid Titanium coupling Non-polymeric First mixed liquid None 10% by mass 89.98% by mass agent binder 90% by mass 0.02% by mass 10% by mass B4 AZO First mixed liquid Titanium coupling Non-polymeric First mixed liquid None 10% by mass 89% by mass agent binder 90% by mass 1% by mass 10% by mass B5 TZO First mixed liquid Titanium coupling Non-polymeric First mixed liquid None 5% by mass 94.5% by mass agent binder 90% by mass 0.5% by mass 10% by mass B6 ATO First mixed liquid None Gelatin Water Water-soluble 18.5% by mass 81.5% by mass 5% by mass 94% by mass cellulose derivative 1% by mass B7 ATO Second mixed liquid Titanium coupling SiO₂ binding agent Second mixed None 6% by mass 85% by mass agent 10% by mass liquid 9.0% by mass 90% by mass B8 ITO Second mixed liquid Titanium coupling SiO₂ binding agent Second mixed None 8% by mass 90% by mass agent 10% by mass liquid 2.0% by mass 90% by mass

TABLE 8 Dispersion Conductive reflective film Coating method Baking treatment Mass composition Transparent Conductive Temp- Classifi- ratio Metal conductive reflective erature Time cation [%] nanoparticles Additives film film Substrate [° C.] [min.] Atmosphere Example B1 55 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air B1 Ni acetate 1% by mass Example B2 60 Ag 96% by mass PVP 3% by mass Spin coating Glass 200 20 air B2 Cu acetate 1% by mass Example B3 70 Ag 89% by mass PVP-dimethylaminoethyl Spin coating Glass 200 20 air B3 Au 5% by mass methacrylate 5% by mass Zn acetate 1% by mass Example B6 80 Ag 72% by mass Methylcellulose Spin coating Glass 200 20 air B4 Pd 24% by mass 3% by mass Mo acetate 1% by mass Example B6 100 Ag 94% by mass Hydroxypropylmethyl- Spin coating Glass 200 20 air B5 Ru 2% by mass cellulose 3% by mass Sn acetate 1% by mass Example B4 120 Ag 92% by mass PVP 3% by mass Dispenser coating Glass 130 20 N₂ B6 Cu 4% by mass Sn acetate 1% by mass Example B5 75 Ag 95.8% by mass PVP 3% by mass Dispenser coating Glass 200 20 air B7 Sn 0.2% by mass Sn acetate 1% by mass Example B1 95 Ag 96.8% by mass PVP 2% by mass Dispenser coating Glass 130 20 air B8 In 0.2% by mass Sn acetate 1% by mass Example B1 110 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air B9 Zn 0.2% by mass Sn acetate 1% by mass Example B1 60 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air B10 Fe 0.2% by mass Zn acetate 1% by mass Example B1 70 Ag 95.8% by mass PVP 3% by mass Screen printing Glass 150 20 air B11 Fe 0.2% by mass Ni acetate 1% by mass Example B1 90 Ag 96.8% by mass PVP 3% by mass Screen printing Glass 150 20 air B12 Mn 0.2% by mass Example B2 120 Ag 90% by mass PVP 9% by mass Knife coating Glass 150 60 air B13 Al₂O₃ 1% by mass Example B2 80 Ag 99% by mass PVP 0.9% by mass Slit coating Glass 400 60 air B14 SiO₂ 0.1% by mass Example B2 70 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air B15 TiO₂ 1% by mass

TABLE 9 Dispersion Conductive reflective film Coating method Baking treatment Mass composition Transparent Conductive Temp- Classifi- ratio Metal conductive reflective erature Time Atmo- cation [%] nanoparticles Additives film film Substrate [° C.] [min.] sphere Example B2 95 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air B16 Cr₂O₃ 1% by mass Example B2 75 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air B17 MnO₂ 1% by mass Example B2 65 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air B18 Fe₂O₃ 0.5% by mass Cr₃O₄ 0.5% by mass Example B2 85 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air B19 Ag₂O 1% by mass Example B3 105 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 Ar B20 Cu(OH)₂ 1% by mass Example B3 75 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B21 ZnO 1% by mass Example B3 80 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B22 MoO₂ 1% by mass Example B3 75 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B23 SnO₂ 1% by mass Example B3 65 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B24 ITO 1% by mass Example B3 55 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B25 ATO 1% by mass Example B3 65 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B26 Methyl silicate 1% by mass Example B7 55 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B27 Titanium isopropoxide 1% by mass Example B7 70 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B28 Ammonium chromate 1% by mass Example B7 85 Ag 95.9% by mass PVP 4% by mass Spin coating PET 150 20 air B29 Mn formate 0.1% by mass Example B7 90 Ag 95.9% by mass PVP 4% by mass Spin coating PET 150 20 air B30 Fe citrate 0.1% by mass

TABLE 10 Dispersion Conductive reflective film Coating method Baking treatment Mass composition Transparent Conductive Temp- Classifi- ratio Metal conductive reflective erature Time cation [%] nanoparticles Additives film film Substrate [° C.] [min.] Atmosphere Example B7 85 Ag 95.9% by mass PVP 4% by mass Spin coating PET 200 20 air B31 Co formate 0.1% by mass Example B8 75 Ag 95% by mass Ni acetate Spin coating PET 150 20 air B32 5% by mass Example B8 65 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air B33 Ag citrate 1% by mass Example B8 60 Ag 95% by mass Cu acetate Spin coating PET 150 20 N₂ B34 5% by mass Example B8 70 Ag 95% by mass Zn acetate Spin coating PET 150 20 air B35 5% by mass Example B8 80 Ag 95% by mass Mn acetate Spin coating PET 150 20 air B36 5% by mass Example B8 90 Ag 95% by mass Sn acetate Die coating PET 150 20 air B37 5% by mass Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example B1 sputter film Ni acetate 1% by mass coating Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example B2 sputter film Ni acetate 1% by mass coating <Comparative Test B1>

The film thickness of the second transparent conductive film within each of the composite films obtained in examples B1 to B37 and comparative examples B1 and B2 was evaluated. The results of the evaluations are listed below in Table 11 and Table 12. Specifically, the thickness of the second transparent conductive film following baking was measured directly from a film cross-section obtained using a SEM (scanning electron microscope S800, manufactured by Hitachi, Ltd.).

<Comparative Test B2>

Each of the substrates having a conductive reflective film formed thereon obtained in examples B1 to B37 and comparative examples B1 and B2 was evaluated for the distribution of holes at the substrate-side contact surface of the conductive reflective film, the back side reflectance and the thickness of the conductive reflective film. The results of these evaluations are listed below in Table 11 and Table 12.

Measurement of the holes was conducted using different methods, depending on whether or not the conductive reflective film was able to be pulled away from the second transparent conductive film.

In those examples where the conductive reflective film was able to be pulled away from the second transparent conductive film, first, an adhesive was applied to a jig having a flat surface, and the jig was pressed against the conductive reflective film bonded to the second transparent conductive film. Following a holding period to allow the adhesive to dry and generate a powerful adhesion, the jig was pulled perpendicularly away from the second transparent conductive film using a pull tester (EZ-TEST, manufactured by Shimadzu Corporation), thereby pulling the conductive reflective film away from the second transparent conductive film.

Subsequently, the uneven surface of the conductive reflective film exposed on the jig that had been peeled away from the second transparent conductive film, which prior to peeling was the substrate-side contact surface of the conductive reflective film, was inspected using an atomic force microscope (AFM). The uneven surface was analyzed, and the average diameter, average depth and number density of the holes that appeared at the film surface were evaluated. The average diameter was determined by measuring the maximum length and minimum length across each opening, and calculating the average value.

Further, another method of pulling the conductive reflective film away from the second transparent conductive film, in which a double-sided tape was bonded to the conductive reflective film, and one end of this tape was then pulled up, thereby peeling the conductive reflective film away from the second conductive reflective film, was also used.

In those examples where the conductive reflective film was not able to be pulled away from the second transparent conductive film, first the conductive reflective film bonded to the second transparent conductive film was processed using a focused ion beam (FIB) to expose a cross-section of the sample. This sample cross-section was inspected using a scanning electron microscope (SEM), and the shape of the interface between the conductive reflective film and the second transparent conductive film was observed. The diameter, average depth and number density of openings within this interface image were evaluated. For each of the evaluated openings, the diameter was taken as being the maximum length across the opening within the cross-sectional image.

Evaluation of the back side reflectance of the conductive reflective film was performed using a combination of an ultraviolet-visible spectrophotometer and an integrating sphere, by measuring the diffuse reflectance of the conductive reflective film at wavelengths of 500 nm and 1,100 nm.

The film thickness of the conductive reflective film was measured from a cross-sectional image obtained using a scanning electron microscope (SEM).

<Comparative Test B3>

The adhesion to the substrate of each of the composite films obtained in examples B1 to B37 and comparative examples B1 and B2 was evaluated. The results of the evaluations are listed in Table 11 and Table 12. The adhesion was evaluated qualitatively on the basis of a peel test in which an adhesive tape was bonded to, and then peeled from, the composite film formed on the substrate. A result of “good” was recorded in those cases where only the adhesive tape peeled from the substrate, a result of “fair” was recorded in those cases where a mixed state was obtained in which only the adhesive tape peeled in some portions and the substrate surface was exposed in other portions, and a result of “poor” was recorded in those cases where peeling of the adhesive tape exposed the entire substrate surface.

TABLE 11 Composite film Conductive reflective film Hole distribution at substrate-side Transparent contact surface Back side conductive film Average Average Number reflectance Thickness diameter depth density [%] Thickness [nm] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example B1 1.0 × 10² 70 70 20 80 95 1.0 × 10² Good Example B2 1.0 × 10² 80 50 10 85 92 5.0 × 10² Good Example B3 1.0 × 10² 89 50 10 81 89 1.0 × 10³ Good Example B4 1.3 × 10² 70 90 5 83 89 1.1 × 10³ Good Example B5 1.3 × 10² 90 50 10 90 97 1.0 × 10³ Good Example B6 1.0 × 10² 90 70 20 85 93 1.2 × 10³ Good Example B7 1.0 × 10² 80 60 15 80 89 1.0 × 10³ Good Example B8 1.0 × 10² 70 45 22 83 90 1.0 × 10³ Good Example B9 1.0 × 10² 90 70 16 82 92 1.9 × 10³ Good Example B10 1.0 × 10² 80 60 20 84 96 1.8 × 10³ Good Example B11 1.0 × 10² 70 50 20 81 93 2.0 × 10³ Good Example B12 1.0 × 10² 60 90 10 83 92 2.0 × 10³ Good Example B13 1.0 × 10² 50 95 5 80 90 2.0 × 10³ Good Example B14 1.0 × 10² 90 80 20 82 91 1.9 × 10³ Good Example B15 1.0 × 10² 70 60 25 85 94 1.0 × 10³ Good Example B16 1.0 × 10² 80 65 15 86 93 1.1 × 10³ Good Example B17 1.0 × 10² 90 60 20 88 92 1.0 × 10³ Good Example B18 1.0 × 10² 40 50 10 83 91 1.2 × 10³ Good Example B19 1.0 × 10² 30 30 10 88 95 1.2 × 10³ Good Example B20 1.0 × 10² 50 50 10 80 96 1.0 × 10³ Good

TABLE 12 Composite film Conductive reflective film Hole distribution at substrate-side Transparent contact surface Back side conductive film Average Average Number reflectance Thickness diameter depth density [%] Thickness [nm] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example B21 1.0 × 10² 80 80 20 82 92 1.0 × 10³ Good Example B22 1.0 × 10² 90 90 28 85 94 1.0 × 10³ Good Example B23 1.0 × 10² 80 75 25 88 96 1.0 × 10³ Good Example B24 1.0 × 10² 50 90 20 87 95 1.1 × 10³ Good Example B25 1.0 × 10² 70 80 15 84 93 1.0 × 10³ Good Example B26 1.0 × 10² 60 90 20 89 95 1.1 × 10³ Good Example B27 1.0 × 10² 40 50 15 86 96 1.0 × 10³ Good Example B28 0.7 × 10² 95 95 12 83 92 1.1 × 10³ Good Example B29 0.7 × 10² 80 85 5 81 90 1.0 × 10³ Good Example B30 0.7 × 10² 55 80 10 86 95 1.0 × 10³ Good Example B31 0.7 × 10² 50 90 5 88 94 1.2 × 10³ Good Example B32 0.7 × 10² 80 80 10 82 92 1.1 × 10³ Good Example B33 0.7 × 10² 70 60 15 84 95 1.0 × 10³ Good Example B34 0.7 × 10² 90 60 20 87 96 1.0 × 10³ Good Example B35 0.7 × 10² 80 90 10 85 95 1.0 × 10³ Good Example B36 0.5 × 10² 80 70 20 83 94 1.1 × 10³ Good Example B37 0.2 × 10² 90 50 10 92 97 1.0 × 10³ Good Comparative 0.7 × 10² 70 70 20 70 80 1.0 × 10² Good example B1 Comparative 2.0 × 10² 70 70 20 75 90 1.0 × 10³ Fair example B2

As is evident from Table 11 and Table 12, of the comparative examples B1 and B2 in which the second transparent conductive film was formed by a sputtering method that represents a vacuum deposition method, comparative example B2 exhibited inferior adhesion to examples B1 to B37. In comparative example B1, the reflectance at 500 nm was a low value of only 70%, and even at 1,100 nm, the reflectance tended to be low. Furthermore, although the reflectance at 1,100 nm in comparative example B2 was a high value of 90%, the reflectance at 500 nm was a comparatively low value of only 75%, confirming that the reflectance varied considerably depending on the wavelength. In contrast, in examples B1 to B37, high reflectance values of not less than 80% were achieved at both the 500 nm wavelength and the 1,100 nm wavelength.

Examples C1 to C32

Transparent conductive film compositions were prepared using the components and amounts listed for the classifications C1 to C8 detailed below in Table 13. The classification numbers from Table 13 for the transparent conductive film compositions used within the various examples are listed in Table 14 and Table 15.

In classification C1, as detailed below in Table 13, a total of 60 g of a mixture composed of 15% by mass of an IZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 72.77% by mass of isopropanol as a dispersion medium, 10% by mass of a mixed liquid of the non-polymeric binders 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione as a binder, and 2.23% by mass of a mixture of indium nitrate and lead acetate (mass ratio 1:1) as a resistance reducer was placed in a 100 cc glass bottle, and using 100 g of zirconia beads with a diameter of 0.3 mm (MICRO HICA, manufactured by Showa Shell Sekiyu K.K.), the mixture was dispersed for 6 hours using a paint shaker, thus yielding a transparent conductive film composition.

In classification C2, as detailed below in Table 13, a transparent conductive film composition was prepared in the same manner as the classification C1, using a mixture composed of 7.5% by mass of an ITO powder having an average particle size of 0.025 μm as a conductive oxide powder, 92.3% by mass of a first mixed liquid composed of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1) as a dispersion medium, 0.038% by mass of the non-polymeric binder 2,4-pentanedione as a binder, and 0.162% by mass of a titanium coupling agent represented by the above formula (14) as a coupling agent.

In classification C3, as detailed below in Table 13, a transparent conductive film composition was prepared in the same manner as the classification C1, using a mixture composed of 5% by mass of an ATO powder having an average particle size of 0.025 μm as a conductive oxide powder, 50.99% by mass of the above first mixed liquid as a dispersion medium, 44% by mass of the non-polymeric binder 2-n-propoxyethanol as a binder, and 0.01% by mass of a titanium coupling agent represented by the above formula (14) as a coupling agent.

In classification C4, as detailed below in Table 13, a transparent conductive film composition was prepared in the same manner as the classification C1, using a mixture composed of 5% by mass of an AZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 74.64% by mass of the above first mixed liquid as a dispersion medium, 20% by mass of a mixed liquid of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1) as a binder, and 0.36% by mass of a titanium coupling agent represented by the above formula (13) as a coupling agent.

In classification C5, as detailed below in Table 13, a transparent conductive film composition was prepared in the same manner as the classification C1, using a mixture composed of 5% by mass of a TZO powder having an average particle size of 0.025 μm as a conductive oxide powder, 93.95% by mass of the above first mixed liquid as a dispersion medium, 0.8% by mass of a mixed liquid of 2-isobutoxyethanol, 2-hexyloxyethanol and n-propyl acetate (mass ratio 4:1:1) as a binder, and 0.25% by mass of a titanium coupling agent represented by the above formula (15) as a coupling agent.

In classification C6, first, an ATO powder having an average particle size of 0.010 μm was suspended in water, the pH of the suspension was adjusted to a value of 7, and the suspension was treated for 30 minutes using a beads mill. Subsequently, hydroxypropylcellulose was added to the suspension as a water-soluble cellulose derivative in a mass ratio of 0.01% relative to the mass of the ATO powder, thus forming a conductive water dispersion. The conductive water dispersion prepared in this manner was adjusted to a solid fraction concentration of 18.5%, and 100 g of this dispersion and 100 g of a 13.2% by mass aqueous solution of gelatin were mixed at 40° C., thus forming a water-based transparent conductive film composition.

In classification C7, as detailed below in Table 13, a transparent conductive film composition was prepared by mixing 5.3% by mass of an ATO powder having an average particle size of 0.025 μm as a conductive oxide powder, 85% by mass of a second mixed liquid composed of ethanol and butanol (mass ratio 98:2) as a dispersion medium, 1.7% by mass of a SiO₂ binding agent as a binder, and 8.0% by mass of a titanium coupling agent represented by the above formula (13) as a coupling agent. The SiO₂ binding agent used as a binder was prepared using a 500 ml four-neck glass flask, by charging the flask with 140 g of tetraethoxysilane and 240 g of ethyl alcohol, adding 1.0 g of 12N-HCl dissolved in 25 g of pure water in a single batch with constant stirring, and then reacting the resulting mixture for 6 hours at 80° C.

In classification C8, as detailed below in Table 13, a transparent conductive film composition was prepared by mixing 8.0% by mass of an ITO powder having an average particle size of 0.025 μm as a conductive oxide powder, 88% by mass of the above second mixed liquid as a dispersion medium, 2.0% by mass of a SiO₂ binding agent as a binder, and 2.0% by mass of a titanium coupling agent represented by the above formula (12) as a coupling agent. The SiO₂ binding agent used as a binder was prepared in the same manner as that described for classification C7.

Next, using the procedure described below, conductive reflective film compositions were prepared.

First, silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution. Further, in a separate preparation, sodium citrate was dissolved in deionized water to prepare an aqueous solution of sodium citrate having a concentration of 26% by mass. A particulate ferrous sulfate was then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of nitrogen gas held at a temperature of 35° C., thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions.

Subsequently, with the stream of nitrogen gas held at 35° C., a magnetic stirrer bar was placed in the reducing agent aqueous solution, and with the reducing agent aqueous solution undergoing constant stirring by rotating the stirrer bar at a rate of 100 rpm, the metal salt aqueous solution was added dropwise to the reducing agent aqueous solution and mixed thoroughly. For this addition, the concentration of each of the solutions was altered so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution was not more than 1/10th of the amount of the reducing agent aqueous solution, thereby ensuring that the reaction temperature was maintained at 40° C. even though the added metal salt aqueous solution was at room temperature. Furthermore, the mixing ratio between the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the molar ratios of both the citrate ions and the ferrous ions within the reducing agent aqueous solution, relative to the total atomic valence number of metal ions within the metal salt aqueous solution, was a 3-fold molar excess. Following completion of the dropwise addition of the metal salt aqueous solution to the reducing agent aqueous solution, stirring of the resulting mixed liquid was continued for a further 15 minutes, thereby generating metal particles within the mixed liquid and forming a metal particles dispersion containing dispersed metal particles. The pH of the metal particles dispersion was 5.5, and the stoichiometric amount of generated metal particles within the dispersion was 5 g/liter.

The thus obtained dispersion was left to stand at room temperature to allow the metal particles within the dispersion to settle out, and the settled metal particle aggregates were isolated by decantation. Deionized water was added to the isolated metal aggregates to form a dispersion, a demineralization treatment was conducted using ultrafiltration, and displacement washing was then performed using methanol, so as to achieve a metal (silver) content of 50% by mass. Subsequently, by using a centrifugal separator with appropriate adjustment of the centrifugal power to separate the comparatively large silver particles having a particle size exceeding 100 nm, a sample was prepared in which silver particles having a primary particle size within a range from 10 to 50 nm represented a number average of 71%. In other words, the silver nanoparticles were prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm was a number average of 71%. The thus obtained silver nanoparticles were chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 3 carbon atoms.

Next, 10 parts by mass of the obtained metal nanoparticles were added to and dispersed within 90 parts by mass of a mixed solution of ethanol and methanol, and by subsequently adding the additives listed below in Table 14 to Table 16 in the proportions shown in Table 14 to Table 16, a series of conductive reflective film compositions was obtained. The metal nanoparticles used in forming these conductive reflective film compositions contained at least 75% of silver nanoparticles.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles were combined as the metal nanoparticles, then the dispersion containing silver nanoparticles produced using the above method was deemed the first dispersion, a dispersion containing metal nanoparticles other than silver nanoparticles was prepared using the same method as the above method used for producing the silver nanoparticles, but with the exception of replacing the silver nitrate with a metal salt listed in Table 14 to Table 16 that is capable of forming metal nanoparticles other than silver nanoparticles, and this dispersion of metal nanoparticles was deemed the second dispersion, and the first dispersion and second dispersion were then mixed together, prior to the addition of additives, in the proportions listed in Table 14 to Table 16, thus forming a conductive reflective film composition.

Finally, composite films were formed using the transparent conductive film compositions and conductive reflective film compositions prepared above. Specifically, first, one of the prepared conductive reflective film compositions was applied to the substrate listed in Table 14 to Table 16 using one of a variety of different coating methods in an amount sufficient to generate a thickness following baking of 10² to 2×10³ nm, and was then dried at a temperature of 25° C. for 5 minutes to form a conductive reflective coating. Subsequently, by baking the substrate having this coating formed thereon under the conditions detailed in Table 14 to Table 16, a conductive reflective film was formed. Next, one of the prepared transparent conductive film compositions was applied to the conductive reflective film using one of a variety of different coating methods in an amount sufficient to generate a thickness following baking of 0.7 to 1.3×10² nm, and was then dried at a temperature of 25° C. for 5 minutes to form a transparent conductive coating. Subsequently, by baking the substrate having this coating formed thereon under the conditions detailed in Table 14 to Table 16, a second transparent conductive film was formed. The above process completes the formation of a composite film on the substrate.

In Table 14 to Table 16, PVP represents a polyvinylpyrrolidone having a Mw of 360,000, and PET represents a polyethylene terephthalate.

Comparative Example C1

With the exception of forming the second transparent conductive film with a thickness of 0.7×10² nm using a sputtering method that represents one example of a vacuum deposition method, a composite film was formed in the same manner as example C1.

Comparative Example C2

With the exception of forming the second transparent conductive film with a thickness of 2.0×10² nm using a sputtering method that represents one example of a vacuum deposition method, a composite film was formed in the same manner as example C1.

TABLE 13 Transparent conductive film composition Classifi- Conductive oxide cation microparticles Dispersion medium Binder Coupling agent Other C1 IZO Isopropanol Non-polymeric binder None Resistance reducer 15% by mass 72.77% by mass 10% by mass 2.23% by mass C2 ITO First mixed liquid Non-polymeric binder Titanium coupling agent None 7.5% by mass 92.3% by mass 0.038% by mass 0.162% by mass C3 ATO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 50.99% by mass 44% by mass 0.01% by mass C4 AZO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 74.64% by mass 20% by mass 0.36% by mass C5 TZO First mixed liquid Non-polymeric binder Titanium coupling agent None 5% by mass 93.95% by mass 0.8% by mass 0.25% by mass C6 ATO Water Gelatin None Water-soluble 9.249% by mass 84.150% by mass 6.600% by mass cellulose derivative 0.001% by mass C7 ATO Second mixed liquid SiO₂ binding agent Titanium coupling agent None 5.3% by mass 85% by mass 1.7% by mass 8.0% by mass C8 ITO Second mixed liquid SiO₂ binding agent Titanium coupling agent None 8.0% by mass 88% by mass 2.0% by mass 2.0% by mass

TABLE 14 Transparent Conductive reflective film Coating method Baking treatment conductive film composition Transparent Conductive Temp- composition Metal conductive reflective erature Time Classification nanoparticles Additives film film Substrate [° C.] [min.] Atmosphere Example C1 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air C1 Ni acetate 1% by mass Example C2 Ag 96% by mass PVP 3% by mass Spin coating Glass 200 20 air C2 Cu acetate 1% by mass Example C3 Ag 89% by mass PVP-dimethylaminoethyl Spin coating Glass 200 20 air C3 Au 5% by mass methacrylate 5% by mass Zn acetate 1% by mass Example C6 Ag 72% by mass Methylcellulose Spin coating Glass 200 20 air C4 Pd 24% by mass 3% by mass Mo acetate 1% by mass Example C6 Ag 94% by mass Hydroxypropylmethyl- Spin coating Glass 200 20 air C5 Ru 2% by mass cellulose 3% by mass Sn acetate 1% by mass Example C4 Ag 92% by mass PVP 3% by mass Dispenser coating Glass 130 20 N₂ C6 Cu 4% by mass Sn acetate 1% by mass Example C5 Ag 95.8% by mass PVP 3% by mass Dispenser coating Glass 200 20 air C7 Sn 0.2% by mass Sn acetate 1% by mass Example C1 Ag 96.8% by PVP 2% by mass Dispenser coating Glass 130 20 air C8 mass Sn acetate 1% by mass In 0.2% by mass Example C1 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air C9 Zn 0.2% by mass Sn acetate 1% by mass Example C1 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air C10 Fe 0.2% by mass Zn acetate 1% by mass Example C1 Ag 95.8% by mass PVP 3% by mass Screen printing Glass 150 20 air C11 Fe 0.2% by mass Ni acetate 1% by mass Example C1 Ag 96.8% by mass PVP 3% by mass Screen printing Glass 150 20 air C12 Mn 0.2% by mass Example C2 Ag 90% by mass PVP 9% by mass Knife coating Glass 150 60 air C13 Al₂O₃ 1% by mass Example C2 Ag 99% by mass PVP 0.9% by mass Slit coating Glass 400 60 air C14 SiO₂ 0.1% by mass Example C2 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air C15 TiO₂ 1% by mass

TABLE 15 Transparent Conductive reflective film Coating method Baking treatment conductive film composition Transparent Conductive Temp- composition Metal conductive reflective erature Time Atmo- Classification nanoparticles Additives film film Substrate [° C.] [min.] sphere Example C2 Ag 95% by PVP 4% by mass Spin coating Glass 150 20 air C16 mass Cr₂O₃ 1% by mass Example C2 Ag 95% by PVP 4% by mass Spin coating Glass 150 20 air C17 mass MnO₂ 1% by mass Example C2 Ag 95% by PVP 4% by mass Spin coating Glass 150 20 air C18 mass Fe₂O₃ 0.5% by mass Cr₃O₄ 0.5% by mass Example C2 Ag 95% by PVP 4% by mass Spin coating Glass 150 20 air C19 mass Ag₂O 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating Glass 150 20 Ar C20 mass Cu(OH)₂ 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C21 mass ZnO 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C22 mass MoO₂ 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C23 mass SnO₂ 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C24 mass ITO 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C25 mass ATO 1% by mass Example C3 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C26 mass Methyl silicate 1% by mass Example C7 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C27 mass Titanium isopropoxide 1% by mass Example C7 Ag 95% by PVP 4% by mass Spin coating PET 150 20 air C28 mass Ammonium chromate 1% by mass Example C7 Ag 95.9% by PVP 4% by mass Spin coating PET 150 20 air C29 mass Mn formate 0.1% by mass Example C7 Ag 95.9% by PVP 4% by mass Spin coating PET 150 20 air C30 mass Fe citrate 0.1% by mass

TABLE 16 Transparent Conductive reflective Coating method conductive film film composition Transparent Conductive Baking treatment composition Metal conductive reflective Temperature Time At- Classification nanoparticles Additives film film Substrate [° C.] [min.] mosphere Example C7 Ag 95.9% by PVP 4% by mass Spin coating PET 200 20 air C31 mass Co formate 0.1% by mass Example C8 Ag 95% by mass Ni acetate Spin coating PET 150 20 air C32 5% by mass Example C8 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air C33 Ag citrate 1% by mass Example C8 Ag 95% by mass Cu acetate Spin coating PET 150 20 N₂ C34 5% by mass Example C8 Ag 95% by mass Zn acetate Spin coating PET 150 20 air C35 5% by mass Example C8 Ag 95% by mass Mn acetate Spin coating PET 150 20 air C36 5% by mass Example C8 Ag 95% by mass Sn acetate Die coating PET 150 20 air C37 5% by mass Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example C1 sputter film Ni acetate 1% by mass coating Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example C2 sputter film Ni acetate 1% by mass coating <Comparative Test C1>

The film thickness of the second transparent conductive film within each of the composite films obtained in examples C1 to C37 and comparative examples C1 and C2 was evaluated. The results of the evaluations are listed below in Table 17 and Table 18. Specifically, the thicknesses of the second transparent conductive film and the conductive reflective film following baking were measured directly from a film cross-section obtained using a SEM (scanning electron microscope S800, manufactured by Hitachi, Ltd.).

<Comparative Test C2>

Each of the substrates having a composite film formed thereon obtained in examples C1 to C37 and comparative examples C1 and C2 was evaluated for the distribution of holes at the contact surface on the side of the second transparent conductive film, the reflectance and the thickness of the conductive reflective film. The results of these evaluations are listed below in Table 17 and Table 18.

Measurement of the holes was conducted by forming the conductive reflective film by applying the conductive reflective film composition to the substrate and performing baking, and then prior to application of the transparent conductive film composition, using an atomic force microscope (AFM) to inspect the uneven surface of the conductive reflective film on which the second transparent conductive film is subsequently formed. The uneven surface was analyzed, and the average diameter, average depth and number density of the holes that appeared at the film surface were evaluated. The average diameter was determined by measuring the maximum length and minimum length across each opening, and calculating the average value.

Evaluation of the reflectance of the conductive reflective film was performed using a combination of an ultraviolet-visible spectrophotometer and an integrating sphere, by measuring the diffuse reflectance of the conductive reflective film at wavelengths of 500 nm and 1,100 nm. The reflectance was measured after formation of the second transparent conductive film, by measuring the reflectance from the upper surface.

The film thickness of the conductive reflective film was measured from a cross-sectional image obtained using a scanning electron microscope (SEM).

<Comparative Test C3>

The adhesion to the substrate of each of the composite films obtained in examples C1 to C37 and comparative examples C1 and C2 was evaluated. The results of the evaluations are listed in Table 17 and Table 18. The adhesion was evaluated qualitatively on the basis of a peel test in which an adhesive tape was bonded to, and then peeled from, the composite film formed on the substrate. A result of “good” was recorded in those cases where only the adhesive tape peeled from the substrate, a result of “fair” was recorded in those cases where a mixed state was obtained in which only the adhesive tape peeled in some portions and the substrate surface was exposed in other portions, and a result of “poor” was recorded in those cases where peeling of the adhesive tape exposed the entire substrate surface.

TABLE 17 Composite film Conductive reflective film Transparent Hole distribution at contact surface on side conductive film of transparent conductive film Reflectance Thickness Average Average depth Number density [%] Thickness [nm] diameter [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example C1 1.0 × 10² 60 70 18 80 92 1.0 × 10² Good Example C2 1.0 × 10² 70 70 8 82 94 5.0 × 10² Good Example C3 1.0 × 10² 80 60 12 86 93 1.0 × 10³ Good Example C4 1.3 × 10² 50 90 14 87 94 1.1 × 10³ Good Example C5 1.3 × 10² 80 50 6 83 92 1.0 × 10³ Good Example C6 1.0 × 10² 70 70 8 81 91 1.2 × 10³ Good Example C7 1.0 × 10² 60 50 12 84 95 1.0 × 10³ Good Example C8 1.0 × 10² 50 50 11 90 96 1.0 × 10³ Good Example C9 1.0 × 10² 80 80 9 89 93 1.9 × 10³ Good Example C10 1.0 × 10² 70 60 17 92 97 1.8 × 10³ Good Example C11 1.0 × 10² 65 40 20 83 90 2.0 × 10³ Good Example C12 1.0 × 10² 60 80 14 84 93 2.0 × 10³ Good Example C13 1.0 × 10² 40 50 12 91 96 2.0 × 10³ Good Example C14 1.0 × 10² 70 70 19 84 93 1.9 × 10³ Good Example C15 1.0 × 10² 60 60 24 91 94 1.0 × 10³ Good Example C16 1.0 × 10² 60 70 23 83 90 1.1 × 10³ Good Example C17 1.0 × 10² 50 50 14 92 95 1.0 × 10³ Good Example C18 1.0 × 10² 40 40 27 91 95 1.2 × 10³ Good Example C19 1.0 × 10² 30 40 25 87 92 1.2 × 10³ Good Example C20 1.0 × 10² 40 30 18 88 95 1.0 × 10³ Good

TABLE 18 Composite film Conductive reflective film Transparent Hole distribution at contact surface on side Back side conductive film of transparent conductive film reflectance Thickness Average Average depth Number density [%] Thickness [nm] diameter [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example C21 1.0 × 10² 70 70 23 89 94 1.0 × 10³ Good Example C22 1.0 × 10² 80 80 21 92 93 1.0 × 10³ Good Example C23 1.0 × 10² 60 60 9 91 95 1.0 × 10³ Good Example C24 1.0 × 10² 50 80 12 93 96 1.1 × 10³ Good Example C25 1.0 × 10² 40 70 13 86 93 1.0 × 10³ Good Example C26 1.0 × 10² 30 90 9 87 92 1.1 × 10³ Good Example C27 1.0 × 10² 40 50 15 88 94 1.0 × 10³ Good Example C28 0.7 × 10² 80 70 21 89 95 1.1 × 10³ Good Example C29 0.7 × 10² 70 80 15 86 93 1.0 × 10³ Good Example C30 0.7 × 10² 40 70 21 85 95 1.0 × 10³ Good Example C31 0.7 × 10² 30 90 19 91 94 1.2 × 10³ Good Example C32 0.7 × 10² 70 60 27 90 94 1.1 × 10³ Good Example C33 0.7 × 10² 50 50 25 86 95 1.0 × 10³ Good Example C34 0.7 × 10² 70 60 24 85 95 1.0 × 10³ Good Example C35 0.7 × 10² 60 80 17 87 96 1.0 × 10³ Good Example C36 0.5 × 10² 50 70 14 86 97 1.1 × 10³ Good Example C37 0.2 × 10² 80 40 15 92 94 1.0 × 10³ Good Comparative 0.7 × 10² 60 70 18 75 83 1.0 × 10² Good example C1 Comparative 2.0 × 10² 60 70 18 78 87 1.0 × 10³ Fair example C2

As is evident from Table 17 and Table 18, of the comparative examples C1 and C2 in which the second transparent conductive film was formed by a sputtering method that represents a vacuum deposition method, comparative example C2 exhibited inferior adhesion to examples C1 to C37. In comparative example C1, the reflectance at 500 nm was a low value of only 75%, and even at 1,100 nm, the reflectance tended to be low. Furthermore, although the reflectance at 1,100 nm in comparative example C2 was a high value of 87%, the reflectance at 500 nm was a comparatively low value of only 78%, confirming that the reflectance varied considerably depending on the wavelength. In contrast, in examples C1 to C37, high reflectance values of not less than 80% were achieved at both the 500 nm wavelength and the 1,100 nm wavelength.

Examples D1 to D32

Conductive oxide microparticles dispersions and binder dispersions were prepared using the components and amounts listed for the classifications D1 to D8 detailed below in Table 19. The classification numbers from Table 19 for the dispersions used within the various examples are listed in Table 20 and Table 21.

In classification D1, as detailed below in Table 19, a total of 60 g of a mixture composed of 20% by mass of an IZO powder having an average particle size of 0.025 μm as conductive oxide microparticles and 80% by mass of isopropanol as a dispersion medium was placed in a 100 cc glass bottle, and using 100 g of zirconia beads with a diameter of 0.3 mm (MICRO HICA, manufactured by Showa Shell Sekiyu K.K.), the mixture was dispersed for 6 hours using a paint shaker, thus yielding a dispersion of conductive oxide microparticles. Further, in a separate preparation, 10% by mass of a mixed liquid of the non-polymeric binders 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione as the binder, 88.2% by mass of isopropanol as a dispersion medium, and 1.8% by mass of a mixture of indium nitrate and lead acetate (mass ratio 1:1) as a resistance reducer were combined and stirred for one hour at room temperature at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification D2, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using a mixture composed of 7.5% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.2% by mass of a titanium coupling agent represented by the above formula (19) as a coupling agent, and 92.3% by mass of a first mixed liquid composed of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1) as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification D1, using 10% by mass of the non-polymeric binder 2,4-pentanedione as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification D3, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using a mixture composed of 10% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.02% by mass of a titanium coupling agent represented by the above formula (19) as a coupling agent, and 89.98% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification D1, using 10% by mass of the non-polymeric binder 2-n-propoxyethanol as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification D4, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using a mixture composed of 10% by mass of an AZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 1% by mass of a titanium coupling agent represented by the above formula (18) as a coupling agent, and 89% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification D1, using 10% by mass of a mixed liquid of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification D5, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using a mixture composed of 5% by mass of a TZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.5% by mass of a titanium coupling agent represented by the above formula (20) as a coupling agent, and 94.5% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification D1, using 10% by mass of a mixed liquid of 2-isobutoxyethanol, 2-hexyloxyethanol and n-propyl acetate (mass ratio 4:1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification D6, first, an ATO powder having an average particle size of 0.010 μm was suspended in water, the pH of the suspension was adjusted to a value of 7, and the suspension was treated for 30 minutes using a beads mill. The above first mixed liquid was added to the treated suspension as a dispersion medium, and the solid fraction concentration was adjusted to 18.5%, thus yielding a dispersion of conductive oxide microparticles. Further, a mixture containing 5% of gelatin as a binder, 1% by mass of hydroxypropylcellulose as a water-soluble cellulose derivative, and 94% by mass of water as the dispersion medium was stirred for one hour at a temperature of 30° C. at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification D7, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using a mixture composed of 6% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 85% by mass of a second mixed liquid composed of ethanol and butanol (mass ratio 98:2) as a dispersion medium, and 9.0% by mass of a titanium coupling agent represented by the above formula (18) as a coupling agent. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium. The SiO₂ binding agent used as a binder was prepared using a 500 ml four-neck glass flask, by charging the flask with 140 g of tetraethoxysilane and 240 g of ethyl alcohol, adding 1.0 g of 12N-HCl dissolved in 25 g of pure water in a single batch with constant stirring, and then reacting the resulting mixture for 6 hours at 80° C.

In classification D8, as detailed below in Table 19, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification D1, using 8% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 2.0% by mass of a titanium coupling agent represented by the above formula (17) as a coupling agent, and 90% by mass of the above second mixed liquid as a dispersion medium. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium.

Next, using the procedure described below, conductive reflective film compositions were prepared.

First, silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution. Further, in a separate preparation, sodium citrate was dissolved in deionized water to prepare an aqueous solution of sodium citrate having a concentration of 26% by mass. A particulate ferrous sulfate was then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of nitrogen gas held at a temperature of 35° C., thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions.

Subsequently, with the stream of nitrogen gas held at 35° C., a magnetic stirrer bar was placed in the reducing agent aqueous solution, and with the reducing agent aqueous solution undergoing constant stirring by rotating the stirrer bar at a rate of 100 rpm, the metal salt aqueous solution was added dropwise to the reducing agent aqueous solution and mixed thoroughly. For this addition, the concentration of each of the solutions was altered so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution was not more than 1/10th of the amount of the reducing agent aqueous solution, thereby ensuring that the reaction temperature was maintained at 40° C. even though the added metal salt aqueous solution was at room temperature. Furthermore, the mixing ratio between the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the molar ratios of both the citrate ions and the ferrous ions within the reducing agent aqueous solution, relative to the total atomic valence number of metal ions within the metal salt aqueous solution, was a 3-fold molar excess. Following completion of the dropwise addition of the metal salt aqueous solution to the reducing agent aqueous solution, stirring of the resulting mixed liquid was continued for a further 15 minutes, thereby generating metal particles within the mixed liquid and forming a metal particles dispersion containing dispersed metal particles. The pH of the metal particles dispersion was 5.5, and the stoichiometric amount of generated metal particles within the dispersion was 5 g/liter.

The thus obtained dispersion was left to stand at room temperature to allow the metal particles within the dispersion to settle out, and the settled metal particle aggregates were isolated by decantation. Deionized water was added to the isolated metal aggregates to form a dispersion, a demineralization treatment was conducted using ultrafiltration, and displacement washing was then performed using methanol, so as to achieve a metal (silver) content of 50% by mass. Subsequently, by using a centrifugal separator with appropriate adjustment of the centrifugal power to separate the comparatively large silver particles having a particle size exceeding 100 nm, a sample was prepared in which silver particles having a primary particle size within a range from 10 to 50 nm represented a number average of 71%. In other words, the silver nanoparticles were prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm was a number average of 71%. The thus obtained silver nanoparticles were chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 3 carbon atoms.

Next, 10 parts by mass of the obtained metal nanoparticles were added to and dispersed within 90 parts by mass of a mixed solution of ethanol and methanol, and by subsequently adding the additives listed below in Table 20 to Table 22 in the proportions shown in Table 20 to Table 22, a series of conductive reflective film compositions was obtained. The metal nanoparticles used in forming these conductive reflective film compositions contained at least 75% of silver nanoparticles.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles were combined as the metal nanoparticles, then the dispersion containing silver nanoparticles produced using the above method was deemed the first dispersion, a dispersion containing metal nanoparticles other than silver nanoparticles was prepared using the same method as the above method used for producing the silver nanoparticles, but with the exception of replacing the silver nitrate with a metal salt listed in Table 20 to Table 22 that is capable of forming metal nanoparticles other than silver nanoparticles, and this dispersion of metal nanoparticles was deemed the second dispersion, and the first dispersion and second dispersion were then mixed together, prior to the addition of additives, in the proportions listed in Table 20 to Table 22, thus forming a conductive reflective film composition.

Finally, composite films were formed using the conductive oxide microparticles dispersions, binder dispersions and conductive reflective film compositions prepared above. Specifically, one of the prepared conductive reflective film compositions was applied to the substrate listed in Table 20 to Table 22 using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.05 to 2.0 μm, and was then dried at a temperature of 25° C. for 5 minutes to form a conductive reflective coating. Next, a prepared dispersion of conductive oxide microparticles was applied to the conductive reflective coating using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.01 to 0.5 μm, and was then dried at a temperature of 25° C. for 5 minutes to form a coating of the conductive oxide microparticles. Next, this coating of conductive oxide microparticles was impregnated with one of the prepared binder dispersions using one of a variety of different coating methods so that, following baking, the entire surface of the conductive oxide microparticles layer was covered with the binder layer, and the binder dispersion was then dried at a temperature of 25° C. for 5 minutes to form a transparent conductive coating. The binder dispersion was applied in such a manner that the mass of the binder component within the binder dispersion, relative to the total mass of microparticles contained within the applied coating of the conductive oxide microparticles was a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) listed below in Table 20 to Table 22. By subsequently performing baking under the conditions detailed below in Table 20 to Table 22, a composite film was formed on the substrate.

In Table 20 to Table 22, PVP represents a polyvinylpyrrolidone having a Mw of 360,000, and PET represents a polyethylene terephthalate.

Comparative Example D1

With the exception of forming the second transparent conductive film with a thickness of 0.7×10² nm using a sputtering method that represents one example of a vacuum deposition method, a composite film was formed in the same manner as example D1.

Comparative Example D2

With the exception of forming the second transparent conductive film with a thickness of 2.0×10² nm using a sputtering method that represents one example of a vacuum deposition method, a composite film was formed in the same manner as example D1.

TABLE 19 Conductive oxide microparticles dispersion Conductive oxide Binder dispersion Classification microparticles Dispersion medium Coupling agent Binder Dispersion medium Other D1 IZO Isopropanol None Non-polymeric binder Isopropanol Resistance reducer 20% by mass 80% by mass 10% by mass 88.2% by mass 1.8% by mass D2 ITO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 7.5% by mass 92.3% by mass 0.2% by mass 10% by mass 90% by mass D3 ATO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 10% by mass 89.98% by mass 0.02% by mass 10% by mass 90% by mass D4 AZO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 10% by mass 89% by mass 1% by mass 10% by mass 90% by mass D5 TZO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 5% by mass 94.5% by mass 0.5% by mass 10% by mass 90% by mass D6 ATO First mixed liquid None Gelatin Water Water-soluble 18.5% by mass 81.5% by mass 5% by mass 94% by mass cellulose derivative % by mass D7 ATO Second mixed liquid Titanium coupling agent SiO₂ binding agent Second mixed None 6% by mass 85% by mass 9.0% by mass 10% by mass liquid 90% by mass D8 ITO Second mixed liquid Titanium coupling agent SiO₂ binding agent Second mixed None 8% by mass 90% by mass 2.0% by mass 10% by mass liquid 90% by mass

TABLE 20 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example D1 60 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air D1 Ni acetate 1% by mass Example D2 50 Ag 96% by mass PVP 3% by mass Spin coating Glass 200 20 air D2 Cu acetate 1% by mass Example D3 55 Ag 89% by mass PVP-dimethylaminoethyl Spin coating Glass 200 20 air D3 Au 5% by mass methacrylate 5% by mass Zn acetate 1% by mass Example D6 60 Ag 72% by mass Methylcellulose Spin coating Glass 200 20 air D4 Pd 24% by mass 3% by mass Mo acetate 1% by mass Example D6 70 Ag 94% by mass Hydroxypropylmethyl- Spin coating Glass 200 20 air D5 Ru 2% by mass cellulose 3% by mass Sn acetate 1% by mass Example D4 55 Ag 92% by mass PVP 3% by mass Dispenser coating Glass 130 20 N₂ D6 Cu 4% by mass Sn acetate 1% by mass Example D5 80 Ag 95.8% by mass PVP 3% by mass Dispenser coating Glass 200 20 air D7 Sn 0.2% by mass Sn acetate 1% by mass Example D1 90 Ag 96.8% by mass PVP 2% by mass Dispenser coating Glass 130 20 air D8 In 0.2% by mass Sn acetate 1% by mass Example D1 100 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air D9 Zn 0.2% by mass Sn acetate 1% by mass Example D1 70 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air D10 Fe 0.2% by mass Zn acetate 1% by mass Example D1 80 Ag 95.8% by mass PVP 3% by mass Screen printing Glass 150 20 air D11 Fe 0.2% by mass Ni acetate 1% by mass Example D1 85 Ag 96.8% by mass PVP 3% by mass Screen printing Glass 150 20 air D12 Mn 0.2% by mass Example D2 75 Ag 90% by mass PVP 9% by mass Knife coating Glass 150 60 air D13 Al₂O₃ 1% by mass Example D2 55 Ag 99% by mass PVP 0.9% by mass Slit coating Glass 400 60 air D14 SiO₂ 0.1% by mass Example D2 65 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air D15 TiO₂ 1% by mass

TABLE 21 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example D2 70 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air D16 Cr₂O₃ 1% by mass Example D2 95 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air D17 MnO₂ 1% by mass Example D2 75 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air D18 Fe₂O₃ 0.5% by mass Cr₃O₄ 0.5% by mass Example D2 80 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air D19 Ag₂O 1% by mass Example D3 85 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 Ar D20 Cu(OH)₂ 1% by mass Example D3 90 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D21 ZnO 1% by mass Example D3 95 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D22 MoO₂ 1% by mass Example D3 60 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D23 SnO₂ 1% by mass Example D3 100 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D24 ITO 1% by mass Example D3 90 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D25 ATO 1% by mass Example D3 55 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D26 Methyl silicate 1% by mass Example D7 80 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D27 Titanium isopropoxide 1% by mass Example D7 90 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D28 Ammonium chromate 1% by mass Example D7 95 Ag 95.9% by mass PVP 4% by mass Mn Spin coating PET 150 20 air D29 formate 0.1% by mass Example D7 105 Ag 95.9% by mass PVP 4% by mass Spin coating PET 150 20 air D30 Fe citrate 0.1% by mass

TABLE 22 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example D7 55 Ag 95.9% by mass PVP 4% by mass Spin coating PET 200 20 air D31 Co formate 0.1% by mass Example D8 70 Ag 95% by mass Ni acetate Spin coating PET 150 20 air D32 5% by mass Example D8 65 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air D33 Ag citrate 1% by mass Example D8 55 Ag 95% by mass Cu acetate Spin coating PET 150 20 N₂ D34 5% by mass Example D8 80 Ag 95% by mass Zn acetate Spin coating PET 150 20 air D35 5% by mass Example D8 70 Ag 95% by mass Mn acetate Spin coating PET 150 20 air D36 5% by mass Example D8 60 Ag 95% by mass Sn acetate Die coating PET 150 20 air D37 5% by mass Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example D1 sputter Ni acetate 1% by mass coating film Comparative ITO Ag 94% by mass PVP 5% by mass Sputter Spin Glass 200 20 air example D2 sputter Ni acetate 1% by mass coating film <Comparative Test D1>

The film thickness of the second transparent conductive film within each of the composite films obtained in examples D1 to D37 and comparative examples D1 and D2 was evaluated. The results of the evaluations are listed below in Table 23 and Table 24. First, the thickness of the second transparent conductive film following baking was measured directly from a film cross-section obtained using a SEM (scanning electron microscope 5800, manufactured by Hitachi, Ltd.).

<Comparative Test D2>

Each of the substrates having a conductive reflective film formed thereon obtained in examples D1 to D37 and comparative examples D1 and D2 was evaluated for the distribution of holes at the substrate-side contact surface, the reflectance and the thickness of the conductive reflective film. The results of these evaluations are listed below in Table 23 and Table 24.

Measurement of the holes was conducted by forming the conductive reflective film by applying the conductive reflective film composition to the substrate and performing baking, and then prior to application of the transparent conductive film composition, using an atomic force microscope (AFM) to inspect the uneven surface of the conductive reflective film on which the second transparent conductive film is subsequently formed. The uneven surface was analyzed, and the average diameter, average depth and number density of the holes that appeared at the film surface were evaluated. The average diameter was determined by measuring the maximum length and minimum length across each opening, and calculating the average value.

Evaluation of the reflectance of the conductive reflective film was performed using a combination of an ultraviolet-visible spectrophotometer and an integrating sphere, by measuring the diffuse reflectance of the conductive reflective film at wavelengths of 500 nm and 1,100 nm. The reflectance was measured after formation of the second transparent conductive film, by measuring the reflectance from the upper surface.

The film thickness of the conductive reflective film was measured from a cross-sectional image obtained using a scanning electron microscope (SEM).

<Comparative Test D3>

The adhesion to the substrate of each of the composite films obtained in examples D1 to D37 and comparative examples D1 and D2 was evaluated. The results of the evaluations are listed in Table 23 and Table 24. The adhesion was evaluated qualitatively on the basis of a peel test in which an adhesive tape was bonded to, and then peeled from, the composite film formed on the substrate. A result of “good” was recorded in those cases where only the adhesive tape peeled from the substrate, a result of “fair” was recorded in those cases where a mixed state was obtained in which only the adhesive tape peeled in some portions and the substrate surface was exposed in other portions, and a result of “poor” was recorded in those cases where peeling of the adhesive tape exposed the entire substrate surface.

TABLE 23 Composite film Conductive reflective film Transparent Hole distribution at substrate-side conductive film contact surface Reflectance Thickness Average Average depth Number density [%] Thickness [nm] diameter [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example D1 1.0 × 10² 60 70 18 82 93 1.0 × 10² Good Example D2 1.0 × 10² 70 70 8 86 93 5.0 × 10² Good Example D3 1.0 × 10² 80 60 12 82 90 1.0 × 10³ Good Example D4 1.3 × 10² 50 90 14 83 90 1.1 × 10³ Good Example D5 1.3 × 10² 80 50 6 88 92 1.0 × 10³ Good Example D6 1.0 × 10² 70 70 8 84 94 1.2 × 10³ Good Example D7 1.0 × 10² 60 50 12 83 91 1.0 × 10³ Good Example D8 1.0 × 10² 50 50 11 85 92 1.0 × 10³ Good Example D9 1.0 × 10² 80 80 9 85 93 1.9 × 10³ Good Example D10 1.0 × 10² 70 60 17 81 95 1.8 × 10³ Good Example D11 1.0 × 10² 65 40 20 82 92 2.0 × 10³ Good Example D12 1.0 × 10² 60 80 14 85 94 2.0 × 10³ Good Example D13 1.0 × 10² 40 50 12 85 92 2.0 × 10³ Good Example D14 1.0 × 10² 70 70 19 83 95 1.9 × 10³ Good Example D15 1.0 × 10² 60 60 24 88 92 1.0 × 10³ Good Example D16 1.0 × 10² 60 70 23 80 93 1.1 × 10³ Good Example D17 1.0 × 10² 50 50 14 82 95 1.0 × 10³ Good Example D18 1.0 × 10² 40 40 27 81 93 1.2 × 10³ Good Example D19 1.0 × 10² 30 40 25 85 96 1.2 × 10³ Good Example D20 1.0 × 10² 40 30 18 84 94 1.0 × 10³ Good

TABLE 24 Composite film Conductive reflective film Transparent Hole distribution at contact surface on side conductive film of transparent conductive film Reflectance Thickness Average Average depth Number density [%] Thickness [nm] diameter [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion Example D21 1.0 × 10² 70 70 23 84 93 1.0 × 10³ Good Example D22 1.0 × 10² 80 80 21 88 93 1.0 × 10³ Good Example D23 1.0 × 10² 60 60 9 82 96 1.0 × 10³ Good Example D24 1.0 × 10² 50 80 12 85 94 1.1 × 10³ Good Example D25 1.0 × 10² 40 70 13 86 95 1.0 × 10³ Good Example D26 1.0 × 10² 30 90 9 85 96 1.1 × 10³ Good Example D27 1.0 × 10² 40 50 15 85 96 1.0 × 10³ Good Example D28 0.7 × 10² 80 70 21 82 90 1.1 × 10³ Good Example D29 0.7 × 10² 70 80 15 84 92 1.0 × 10³ Good Example D30 0.7 × 10² 40 70 21 85 94 1.0 × 10³ Good Example D31 0.7 × 10² 30 90 19 85 95 1.2 × 10³ Good Example D32 0.7 × 10² 70 60 27 83 93 1.1 × 10³ Good Example D33 0.7 × 10² 50 50 25 86 96 1.0 × 10³ Good Example D34 0.7 × 10² 70 60 24 83 95 1.0 × 10³ Good Example D35 0.7 × 10² 60 80 17 81 93 1.0 × 10³ Good Example D36 0.5 × 10² 50 70 14 84 92 1.1 × 10³ Good Example D37 0.2 × 10² 80 40 15 87 97 1.0 × 10³ Good Comparative 0.7 × 10² 60 70 18 75 83 1.0 × 10² Good example D1 Comparative 2.0 × 10² 60 70 18 78 87 1.0 × 10³ Fair example D2

As is evident from Table 23 and Table 24, of the comparative examples D1 and D2 in which the second transparent conductive film was formed by a sputtering method that represents a vacuum deposition method, comparative example D2 exhibited inferior adhesion to examples D1 to D37. In comparative example D1, the reflectance at 500 nm was a low value of only 75%, and even at 1,100 nm, the reflectance tended to be low. Furthermore, although the reflectance at 1,100 nm in comparative example D2 was a high value of 87%, the reflectance at 500 nm was a comparatively low value of only 78%, confirming that the reflectance varied considerably depending on the wavelength. In contrast, in examples D1 to D37, high reflectance values of not less than 80% were achieved at both the 500 nm wavelength and the 1,100 nm wavelength.

Examples E1 to E32

Conductive oxide microparticles dispersions and binder dispersions were prepared using the components and amounts listed for the classifications E1 to E8 detailed below in Table 25. The classification numbers from Table 25 for the dispersions used within the various examples are listed in Table 26 and Table 27.

In classification E1, as detailed below in Table 25, a total of 60 g of a mixture composed of 20% by mass of an IZO powder having an average particle size of 0.025 μm as conductive oxide microparticles and 80% by mass of isopropanol as a dispersion medium was placed in a 100 cc glass bottle, and using 100 g of zirconia beads with a diameter of 0.3 mm (MICRO HICA, manufactured by Showa Shell Sekiyu K.K.), the mixture was dispersed for 6 hours using a paint shaker, thus yielding a dispersion of conductive oxide microparticles. Further, in a separate preparation, 10% by mass of a mixed liquid of the non-polymeric binders 2-n-butoxyethanol and 3-isopropyl-2,4-pentanedione as the binder, 88.2% by mass of isopropanol as a dispersion medium, and 1.8% by mass of a mixture of indium nitrate and lead acetate (mass ratio 1:1) as a resistance reducer were combined and stirred for one hour at room temperature at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification E2, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using a mixture composed of 7.5% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.2% by mass of a titanium coupling agent represented by the above formula (24) as a coupling agent, and 92.3% by mass of a first mixed liquid composed of isopropanol, ethanol and N,N-dimethylformamide (mass ratio 4:2:1) as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification E1, using 10% by mass of the non-polymeric binder 2,4-pentanedione as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification E3, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using a mixture composed of 10% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.02% by mass of a titanium coupling agent represented by the above formula (24) as a coupling agent, and 89.98% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification E1, using 10% by mass of the non-polymeric binder 2-n-propoxyethanol as the binder and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification E4, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using a mixture composed of 10% by mass of an AZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 1% by mass of a titanium coupling agent represented by the above formula (23) as a coupling agent, and 89% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification E1, using 10% by mass of a mixed liquid of 2,2-dimethyl-3,5-hexanedione and isopropyl acetate (mass ratio 1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification E5, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using a mixture composed of 5% by mass of a TZO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 0.5% by mass of a titanium coupling agent represented by the above formula (25) as a coupling agent, and 94.5% by mass of the above first mixed liquid as a dispersion medium. Further, a binder dispersion was prepared in the same manner as the classification E1, using 10% by mass of a mixed liquid of 2-isobutoxyethanol, 2-hexyloxyethanol and n-propyl acetate (mass ratio 4:1:1) as the binder, and 90% by mass of the above first mixed liquid as a dispersion medium.

In classification E6, first, an ATO powder having an average particle size of 0.010 μm was suspended in water, the pH of the suspension was adjusted to a value of 7, and the suspension was treated for 30 minutes using a beads mill. The above first mixed liquid was added to the treated suspension as a dispersion medium, and the solid fraction concentration was adjusted to 18.5%, thus yielding a dispersion of conductive oxide microparticles. Further, a mixture containing 5% of gelatin as a binder, 1% by mass of hydroxypropylcellulose as a water-soluble cellulose derivative, and 94% by mass of water as the dispersion medium was stirred for one hour at a temperature of 30° C. at a rotational rate of 200 rpm, thus forming a binder dispersion.

In classification E7, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using a mixture composed of 6% by mass of an ATO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 85% by mass of a second mixed liquid composed of ethanol and butanol (mass ratio 98:2) as a dispersion medium, and 9.0% by mass of a titanium coupling agent represented by the above formula (23) as a coupling agent. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium. The SiO₂ binding agent used as a binder was prepared using a 500 ml four-neck glass flask, by charging the flask with 140 g of tetraethoxysilane and 240 g of ethyl alcohol, adding 1.0 g of 12N-HCl dissolved in 25 g of pure water in a single batch with constant stirring, and then reacting the resulting mixture for 6 hours at 80° C.

In classification E8, as detailed below in Table 25, a dispersion of conductive oxide microparticles was prepared in the same manner as the classification E1, using 8% by mass of an ITO powder having an average particle size of 0.025 μm as the conductive oxide microparticles, 2.0% by mass of a titanium coupling agent represented by the above formula (22) as a coupling agent, and 90% by mass of the above second mixed liquid as a dispersion medium. Further, in a separate preparation, a binder dispersion was prepared by mixing 10% by mass of a SiO₂ binding agent as a binder and 90% by mass of the above second mixed liquid as a dispersion medium.

Next, using the procedure described below, conductive reflective film compositions were prepared.

First, silver nitrate was dissolved in deionized water to prepare a metal salt aqueous solution. Further, in a separate preparation, sodium citrate was dissolved in deionized water to prepare an aqueous solution of sodium citrate having a concentration of 26% by mass. A particulate ferrous sulfate was then added directly to, and dissolved in, the sodium citrate aqueous solution under a stream of nitrogen gas held at a temperature of 35° C., thus preparing a reducing agent aqueous solution containing a 3:2 molar ratio of citrate ions and ferrous ions.

Subsequently, with the stream of nitrogen gas held at 35° C., a magnetic stirrer bar was placed in the reducing agent aqueous solution, and with the reducing agent aqueous solution undergoing constant stirring by rotating the stirrer bar at a rate of 100 rpm, the metal salt aqueous solution was added dropwise to the reducing agent aqueous solution and mixed thoroughly. For this addition, the concentration of each of the solutions was altered so that the amount of the metal salt aqueous solution added to the reducing agent aqueous solution was not more than 1/10th of the amount of the reducing agent aqueous solution, thereby ensuring that the reaction temperature was maintained at 40° C. even though the added metal salt aqueous solution was at room temperature. Furthermore, the mixing ratio between the reducing agent aqueous solution and the metal salt aqueous solution was adjusted so that the molar ratios of both the citrate ions and the ferrous ions within the reducing agent aqueous solution, relative to the total atomic valence number of metal ions within the metal salt aqueous solution, was a 3-fold molar excess. Following completion of the dropwise addition of the metal salt aqueous solution to the reducing agent aqueous solution, stirring of the resulting mixed liquid was continued for a further 15 minutes, thereby generating metal particles within the mixed liquid and forming a metal particles dispersion containing dispersed metal particles. The pH of the metal particles dispersion was 5.5, and the stoichiometric amount of generated metal particles within the dispersion was 5 g/liter.

The thus obtained dispersion was left to stand at room temperature to allow the metal particles within the dispersion to settle out, and the settled metal particle aggregates were isolated by decantation. Deionized water was added to the isolated metal aggregates to form a dispersion, a demineralization treatment was conducted using ultrafiltration, and displacement washing was then performed using methanol, so as to achieve a metal (silver) content of 50% by mass. Subsequently, by using a centrifugal separator with appropriate adjustment of the centrifugal power to separate the comparatively large silver particles having a particle size exceeding 100 nm, a sample was prepared in which silver particles having a primary particle size within a range from 10 to 50 nm represented a number average of 71%. In other words, the silver nanoparticles were prepared such that relative to 100% of all the silver nanoparticles, the proportion of silver nanoparticles having a primary particle size within a range from 10 to 50 nm was a number average of 71%. The thus obtained silver nanoparticles were chemically modified with a protective agent having an organic molecular main chain with a carbon skeleton containing 3 carbon atoms.

Next, 10 parts by mass of the obtained metal nanoparticles were added to and dispersed within 90 parts by mass of a mixed solution of ethanol and methanol, and by subsequently adding the additives listed below in Table 26 to Table 28 in the proportions shown in Table 26 to Table 28, a series of conductive reflective film compositions was obtained. The metal nanoparticles used in forming these conductive reflective film compositions contained at least 75% of silver nanoparticles.

In those cases where silver nanoparticles and metal nanoparticles other than silver nanoparticles were combined as the metal nanoparticles, then the dispersion containing silver nanoparticles produced using the above method was deemed the first dispersion, a dispersion containing metal nanoparticles other than silver nanoparticles was prepared using the same method as the above method used for producing the silver nanoparticles, but with the exception of replacing the silver nitrate with a metal salt listed in Table 26 to Table 28 that is capable of forming metal nanoparticles other than silver nanoparticles, and this dispersion of metal nanoparticles was deemed the second dispersion, and the first dispersion and second dispersion were then mixed together, prior to the addition of additives, in the proportions listed in Table 26 to Table 28, thus forming a conductive reflective film composition.

Finally, composite films were formed using the conductive oxide microparticles dispersions, binder dispersions and conductive reflective film compositions prepared above. Specifically, first, one of the prepared dispersions of conductive oxide microparticles was applied to the substrate listed in Table 26 to Table 28 using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.01 to 0.5 μm, and was then dried at a temperature of 25° C. for 5 minutes to form a coating of the conductive oxide microparticles. Next, this coating of conductive oxide microparticles was impregnated with one of the prepared binder dispersions using one of a variety of different coating methods so that the binder dispersion penetrated to a predetermined depth of the conductive oxide microparticles coating, and the binder dispersion was then dried at a temperature of 25° C. for 5 minutes to form a transparent conductive coating. The binder dispersion was applied in such a manner that the mass of the binder component within the binder dispersion, relative to the total mass of microparticles contained within the applied coating of the conductive oxide microparticles was a mass ratio (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) listed below in Table 26 to Table 28. Subsequently, one of the prepared conductive reflective film compositions was applied to the transparent conductive coating using one of a variety of different coating methods in an amount sufficient to generate a film thickness following baking of 0.05 to 2.0 and was then dried at a temperature of 25° C. for 5 minutes to form a conductive reflective coating. By subsequently performing baking under the conditions detailed in Table 26 to Table 28, a composite film was formed on the substrate.

Furthermore, thin-film solar cells were formed by forming a composite film according to the fifth embodiment of the present invention on top of the photovoltaic layer of a superstrate solar cell. Specifically, as illustrated in FIG. 9, a microcrystalline silicon layer having a thickness of 1.7 μm that functions as a photovoltaic layer 533 was first deposited by plasma CVD on a SnO₂ film 532 having a textured structure. Next, using the same conditions as those described above for forming a composite film on a substrate, a composite film composed of a second transparent conductive film 534 and a conductive reflective film 535 was formed on top of the photovoltaic layer 533. Subsequently, a mask pattern was placed over the surface of the conductive reflective film 535, a magnetron sputtering method was used to deposit an ITO film 536 of thickness 200 nm, and a laser patterning method was then used to remove those portions where the ITO film 536 had not been deposited, thus forming a thin-film solar cell of the type illustrated in the top view of FIG. 10. In FIG. 10, each of the regions indicated by the symbol 551 functions as an individual cell of the thin-film solar cell 550.

In Table 26 to Table 28, PVP represents a polyvinylpyrrolidone having a Mw of 360,000, and PET represents a polyethylene terephthalate.

Comparative Example E1

With the exception of applying the binder dispersion such that the mass ratio relative to the total mass of conductive oxide microparticles contained within the applied coating of the conductive oxide microparticles (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) was 150%, a composite film was formed on a substrate in the same manner as example E1.

Comparative Example E2

With the exception of applying the binder dispersion such that the mass ratio relative to the total mass of conductive oxide microparticles contained within the applied coating of the conductive oxide microparticles (mass of binder component within applied binder dispersion/mass of conductive oxide microparticles) was 200%, a composite film was formed on a substrate in the same manner as example E1.

TABLE 25 Conductive oxide microparticles dispersion Conductive oxide Binder dispersion Classification microparticles Dispersion medium Coupling agent Binder Dispersion medium Other E1 IZO Isopropanol None Non-polymeric binder Isopropanol Resistance reducer 20% by mass 80% by mass 10% by mass 88.2% by mass 1.8% by mass E2 ITO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 7.5% by mass 92.3% by mass 0.2% by mass 10% by mass 90% by mass E3 ATO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 10% by mass 89.98% by mass 0.02% by mass 10% by mass 90% by mass E4 AZO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 10% by mass 89% by mass 1% by mass 10% by mass 90% by mass E5 TZO First mixed liquid Titanium coupling agent Non-polymeric binder First mixed liquid None 5% by mass 94.5% by mass 0.5% by mass 10% by mass 90% by mass E6 ATO First mixed liquid None Gelatin Water Water-soluble 18.5% by mass 81.5% by mass 5% by mass 94% by mass cellulose derivative 1% by mass E7 ATO Second mixed liquid Titanium coupling agent SiO₂ binding agent Second mixed None 6% by mass 85% by mass 9.0% by mass 10% by mass liquid 90% by mass E8 ITO Second mixed liquid Titanium coupling agent SiO₂ binding agent Second mixed None 8% by mass 90% by mass 2.0% by mass 10% by mass liquid 90% by mass

TABLE 26 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example E1 40 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air E1 Ni acetate 1% by mass Example E2 30 Ag 96% by mass PVP 3% by mass Spin coating Glass 200 20 air E2 Cu acetate 1% by mass Example E3 40 Ag 89% by mass PVP-dimethylaminoethyl Spin coating Glass 200 20 air E3 Au 5% by mass methacrylate 5% by mass Zn acetate 1% by mass Example E6 25 Ag 72% by mass Methylcellulose Spin coating Glass 200 20 air E4 Pd 24% by mass 3% by mass Mo acetate 1% by mass Example E6 20 Ag 94% by mass Hydroxypropylmethyl- Spin coating Glass 200 20 air E5 Ru 2% by mass cellulose 3% by mass Sn acetate 1% by mass Example E4 30 Ag 92% by mass PVP 3% by mass Dispenser coating Glass 130 20 N2 E6 Cu 4% by mass Sn acetate 1% by mass Example E5 30 Ag 95.8% by mass PVP 3% by mass Dispenser coating Glass 200 20 air E7 Sn 0.2% by mass Sn acetate 1% by mass Example E1 30 Ag 96.8% by mass PVP 2% by mass Dispenser coating Glass 130 20 air E8 In 0.2% by mass Sn acetate 1% by mass Example E1 40 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air E9 Zn 0.2% by mass Sn acetate 1% by mass Example E1 30 Ag 95.8% by mass PVP 3% by mass Offset printing Glass 320 20 air E10 Fe 0.2% by mass Zn acetate 1% by mass Example E1 40 Ag 95.8% by mass PVP 3% by mass Screen printing Glass 150 20 air E11 Fe 0.2% by mass Ni acetate 1% by mass Example E1 30 Ag 96.8% by mass PVP 3% by mass Screen printing Glass 150 20 air E12 Mn 0.2% by mass Example E2 15 Ag 90% by mass PVP 9% by mass Knife coating Glass 150 60 air E13 Al₂O₃ 1% by mass Example E2 40 Ag 99% by mass PVP 0.9% by mass Slit coating Glass 400 60 air E14 SiO₂ 0.1% by mass Example E2 20 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air E15 TiO₂ 1% by mass

TABLE 27 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example E2 30 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air E16 Cr₂O₃ 1% by mass Example E2 10 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air E17 MnO₂ 1% by mass Example E2 45 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air E18 Fe₂O₃ 0.5% by mass Cr₃O₄ 0.5% by mass Example E2 35 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 air E19 Ag₂O 1% by mass Example E3 25 Ag 95% by mass PVP 4% by mass Spin coating Glass 150 20 Ar E20 Cu(OH)₂ 1% by mass Example E3 45 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E21 ZnO 1% by mass Example E3 35 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E22 MoO₂ 1% by mass Example E3 20 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E23 SnO₂ 1% by mass Example E3 25 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E24 ITO 1% by mass Example E3 15 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E25 ATO 1% by mass Example E3 25 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E26 Methyl silicate 1% by mass Example E7 30 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E27 Titanium isopropoxide 1% by mass Example E7 40 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E28 Ammonium chromate 1% by mass Example E7 35 Ag 95.9% by mass PVP 4% by mass Mn Spin coating PET 150 20 air E29 formate 0.1% by mass Example E7 15 Ag 95.9% by mass PVP 4% by mass Spin coating PET 150 20 air E30 Fe citrate 0.1% by mass

TABLE 28 Dispersion Conductive reflective Coating method Mass film composition Transparent Conductive Baking treatment Classi- ratio Metal conductive reflective Temperature Time Atmos- fication [%] nanoparticles Additives film film Substrate [° C.] [min.] phere Example E7 25 Ag 95.9% by mass PVP 4% by mass Spin coating PET 200 20 air E31 Co formate 0.1% by mass Example E8 20 Ag 95% by mass Ni acetate Spin coating PET 150 20 air E32 5% by mass Example E8 35 Ag 95% by mass PVP 4% by mass Spin coating PET 150 20 air E33 Ag citrate 1% by mass Example E8 25 Ag 95% by mass Cu acetate Spin coating PET 150 20 N₂ E34 5% by mass Example E8 45 Ag 95% by mass Zn acetate Spin coating PET 150 20 air E35 5% by mass Example E8 35 Ag 95% by mass Mn acetate Spin coating PET 150 20 air E36 5% by mass Example E8 20 Ag 95% by mass Sn acetate Die coating PET 150 20 air E37 5% by mass Comparative E1 150 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air example E1 Ni acetate 1% by mass Comparative E5 200 Ag 94% by mass PVP 5% by mass Spin coating Glass 200 20 air example E2 Ni acetate 1% by mass <Comparative Test E1>

The film thickness of the second transparent conductive film within each of the composite films obtained in examples E1 to E37 and comparative examples E1 and E2 were evaluated. The results of the evaluations are listed below in Table 29 and Table 30. First, the thickness of the second transparent conductive film following baking was measured directly from a film cross-section obtained using a SEM (scanning electron microscope S800, manufactured by Hitachi, Ltd.). Further, the proportion of protrusion of the second layer within the second transparent conductive film was also measured. Specifically, each sample was processed using a focused ion beam (FIB) method to expose a sample cross-section, and this sample cross-section was then inspected using a scanning electron microscope (SEM).

<Comparative Test E2>

Each of the substrates having a conductive reflective film formed thereon obtained in examples E1 to E37 and comparative examples E1 and E2 was evaluated for the distribution of holes at the substrate-side contact surface, the back side reflectance and the thickness of the conductive reflective film. The results of these evaluations are listed below in Table 29 and Table 30.

Measurement of the holes was conducted using different methods, depending on whether or not the conductive reflective film was able to be pulled away from the second transparent conductive film.

In those examples where the conductive reflective film was able to be pulled away from the second transparent conductive film, first, an adhesive was applied to a jig having a flat surface, and the jig was pressed against the conductive reflective film bonded to the second transparent conductive film. Following a holding period to allow the adhesive to dry and generate a powerful adhesion, the jig was pulled perpendicularly away from the second transparent conductive film using a pull tester (EZ-TEST, manufactured by Shimadzu Corporation), thereby pulling the conductive reflective film away from the second transparent conductive film.

Subsequently, the uneven surface of the conductive reflective film exposed on the jig that had been peeled away from the second transparent conductive film, which prior to peeling was the substrate-side contact surface of the conductive reflective film, was inspected using an atomic force microscope (AFM). The uneven surface was analyzed, and the average diameter, average depth and number density of the holes that appeared at the film surface were evaluated. The average diameter was determined by measuring the maximum length and minimum length across each opening, and calculating the average value.

Further, another method of pulling the conductive reflective film away from the second transparent conductive film, in which a double-sided tape was bonded to the conductive reflective film, and one end of this tape was then pulled up, thereby peeling the conductive reflective film away from the second conductive reflective film, was also used.

In those examples where the conductive reflective film was not able to be pulled away from the second transparent conductive film, first the conductive reflective film bonded to the second transparent conductive film was processed using a focused ion beam (FIB) to expose a cross-section of the sample. This sample cross-section was inspected using a scanning electron microscope (SEM), and the shape of the interface between the conductive reflective film and the second transparent conductive film was observed. The diameter, average depth and number density of openings within this interface image were evaluated. For each of the evaluated openings, the diameter was taken as being the maximum length across the opening within the cross-sectional image.

Evaluation of the back side reflectance of the conductive reflective film was performed using a combination of an ultraviolet-visible spectrophotometer and an integrating sphere, by measuring the diffuse reflectance of the conductive reflective film at wavelengths of 500 nm and 1,100 nm.

The film thickness of the conductive reflective film was measured from a cross-sectional image obtained using a scanning electron microscope (SEM).

<Comparative Test E3>

The adhesion to the substrate of each of the composite films obtained in examples E1 to E37 and comparative examples E1 and E2 was evaluated. The results of the evaluations are listed below in Table 29 and Table 30. The adhesion was evaluated qualitatively on the basis of a peel test in which an adhesive tape was bonded to, and then peeled from, the composite film formed on the substrate. A result of “good” was recorded in those cases where only the adhesive tape peeled from the substrate, a result of “fair” was recorded in those cases where a mixed state was obtained in which only the adhesive tape peeled in some portions and the substrate surface was exposed in other portions, and a result of “poor” was recorded in those cases where peeling of the adhesive tape exposed the entire substrate surface.

<Comparative Test E4>

Each of the individual cells 551 of a thin-film solar cell illustrated in FIG. 10 obtained in examples E1 to E37 and comparative examples E1 and E2 was evaluated and a cell failure rate was recorded. The results are shown below in Table 29 and Table 30. Specifically, as illustrated in FIG. 9, a laser patterning method was used to remove the photovoltaic layer 533 and the like, a probe 537 was provided to connect the surface of the exposed SnO₂ film 532 and the ITO film 536, and an I-V tracer 538 was installed between the two films. In this state, the electric power generated when a light of AM 1.5 was irradiated with an intensity of 100 W/cm² onto the solar cell from the side of the glass substrate 531 was evaluated. A fill factor result of 0.5 or less was deemed a fail, and the number of individual cell failures relative to the total individual cell count of 50 was reported as a cell failure rate for each of the examples and comparative examples.

TABLE 29 Composite film Transparent conductive film Degree of Conductive reflective film protrusion Hole distribution at of substrate-side contact surface second Average Average Number Reflectance Thickness layer diameter depth density [%] Thickness Cell failure [nm] [%] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion rate [%] Example E1 1.0 × 10² 5 70 70 20 85 94 1.0 × 10² Good 5% or less Example E2 1.0 × 10² 10 80 50 10 83 91 5.0 × 10² Good 5% or less Example E3 1.0 × 10² 5 89 50 10 87 96 1.0 × 10³ Good 5% or less Example E4 1.3 × 10² 15 70 90 5 83 95 1.1 × 10³ Good 5% or less Example E5 1.3 × 10² 7 90 50 10 82 93 1.0 × 10³ Good 5% or less Example E6 1.0 × 10² 10 90 70 20 84 93 1.2 × 10³ Good 5% or less Example E7 1.0 × 10² 15 80 60 15 83 92 1.0 × 10³ Good 5% or less Example E8 1.0 × 10² 10 70 45 22 81 91 1.0 × 10³ Good 5% or less Example E9 1.0 × 10² 2 90 70 16 86 95 1.9 × 10³ Good 5% or less Example E10 1.0 × 10² 15 80 60 20 85 97 1.8 × 10³ Good 5% or less Example E11 1.0 × 10² 3 70 50 20 86 92 2.0 × 10³ Good 5% or less Example E12 1.0 × 10² 10 60 90 10 82 89 2.0 × 10³ Good 5% or less Example E13 1.0 × 10² 30 50 95 5 80 90 2.0 × 10³ Good 5% or less Example E14 1.0 × 10² 2 90 80 20 84 92 1.9 × 10³ Good 5% or less Example E15 1.0 × 10² 15 70 60 25 83 93 1.0 × 10³ Good 5% or less Example E16 1.0 × 10² 10 80 65 15 85 94 1.1 × 10³ Good 5% or less Example E17 1.0 × 10² 25 90 60 20 80 90 1.0 × 10³ Good 5% or less Example E18 1.0 × 10² 1 40 50 10 85 95 1.2 × 10³ Good 5% or less Example E19 1.0 × 10² 8 30 30 10 86 96 1.2 × 10³ Good 5% or less Example E20 1.0 × 10² 10 50 50 10 82 92 1.0 × 10³ Good 5% or less

TABLE 30 Composite film Transparent conductive film Degree of Conductive reflective film protrusion Hole distribution at of substrate-side contact surface second Average Average Number Reflectance Thickness layer diameter depth density [%] Thickness Cell failure [nm] [%] [nm] [nm] [holes/μm²] 500 nm 1100 nm [nm] Adhesion rate [%] Example E21 1.0 × 10² 2 80 80 20 83 95 1.0 × 10³ Good 5% or less Example E22 1.0 × 10² 10 90 90 28 81 97 1.0 × 10³ Good 5% or less Example E23 1.0 × 10² 25 80 75 25 86 97 1.0 × 10³ Good 5% or less Example E24 1.0 × 10² 20 50 90 20 83 94 1.1 × 10³ Good 5% or less Example E25 1.0 × 10² 10 70 80 15 85 92 1.0 × 10³ Good 5% or less Example E26 1.0 × 10² 6 60 90 20 80 96 1.1 × 10³ Good 5% or less Example E27 1.0 × 10² 10 40 50 15 88 95 1.0 × 10³ Good 5% or less Example E28 0.7 × 10² 5 95 95 12 88 90 1.1 × 10³ Good 5% or less Example E29 0.7 × 10² 10 80 85 5 84 92 1.0 × 10³ Good 5% or less Example E30 0.7 × 10² 30 55 80 10 82 94 1.0 × 10³ Good 5% or less Example E31 0.7 × 10² 20 50 90 5 84 90 1.2 × 10³ Good 5% or less Example E32 0.7 × 10² 20 80 80 10 81 91 1.1 × 10³ Good 5% or less Example E33 0.7 × 10² 15 70 60 15 86 94 1.0 × 10³ Good 5% or less Example E34 0.7 × 10² 20 90 60 20 85 92 1.0 × 10³ Good 5% or less Example E35 0.5 × 10² 1 80 90 10 89 92 1.0 × 10³ Good 5% or less Example E36 0.3 × 10² 10 80 70 20 83 93 1.1 × 10³ Good 5% or less Example E37 0.2 × 10² 20 90 50 10 85 94 1.0 × 10³ Good 5% or less Comparative 0.5 × 10² 0 70 70 20 86 80 1.0 × 10² Good 20% example E1 Comparative 1.0 × 10² 0 70 70 20 87 90 1.0 × 10³ Fair 50% example E2

As is evident from Table 29 and Table 30, of the comparative examples E1 and E2, comparative example E2 exhibited inferior adhesion to examples E1 to E37. In comparative example E1 and E2, although the reflectance values at 500 nm and the reflectance values at 1,100 nm were high values similar to those obtained in examples E1 to E37, the cell failure rate was very high in both cases. In contrast, in examples E1 to E37, excellent cell failure rates of 5% or less were obtained.

INDUSTRIAL APPLICABILITY

One aspect of the present invention is extremely useful as a technique for producing, at low cost, an electrode which is ideal for use within a superstrate solar cell in which a transparent substrate such as glass functions as the light receiving surface, wherein the electrode is provided on the opposite side from the light receiving surface.

Another aspect of the present invention is extremely useful as a technique for producing, at low cost, an electrode that is provided on the back side (the opposite side from the light receiving surface) of a so-called substrate solar cell in which the opposite surface from the substrate of glass or the like functions as the light receiving surface.

Furthermore, by employing the present invention, transparent conductive films and conductive reflective films that have conventionally been formed by vacuum deposition methods can be formed by using coating and baking processes, meaning a dramatic reduction in production costs can be expected. 

The invention claimed is:
 1. A composite film for a superstrate thin-film solar cell, having two layers composed of a transparent conductive film formed on a photovoltaic layer of a superstrate thin-film solar cell, and a conductive reflective film formed on top of said transparent conductive film, wherein said transparent conductive film is formed by using a wet coating method to apply a transparent conductive film composition comprising microparticles of a conductive oxide and either one or both of a polymeric binder and a non-polymeric binder that cure upon heating, said polymeric binder is one or more selected from acrylic resins, polycarbonates, polyesters, alkyd resins, polyurethanes, acrylic urethanes, polystyrenes, polyacetals, polyamides, polyvinyl alcohols, polyvinyl acetates, and celluloses, said non-polymeric binder is one or more selected from metal soaps, metal complexes, metal alkoxides, 2-alkoxyethanols, β-diketones, and alkyl acetates, metal contained within said metal soap, said metal complex, or said metal alkoxide is aluminum, titanium, chromium, manganese, iron, cobalt, nickel, silver, copper, zinc, molybdenum, tin, indium, or antimony, said conductive reflective film is formed by using a wet coating method to apply a conductive reflective film composition comprising metal nanoparticles, an average diameter of holes occurring at a surface of said conductive reflective film in direct contact with said transparent conductive film is not more than 100 nm, an average depth at which said holes are positioned is not more than 100 nm, and a number density of said holes is not more than 30 holes/μm², said conductive reflective film comprises one or more materials selected from the group consisting of polyvinylpyrrolidones, polyvinylpyrrolidone copolymers and water-soluble celluloses, and said composite film is manufactured by a method comprising: forming a transparent conductive coating by applying said transparent conductive film composition to said photovoltaic layer and drying an applied coating at a temperature of 20 to 120° C.; forming a conductive reflective coating by applying said conductive reflective film composition to said transparent conductive coating and drying an applied coating at a temperature of 20 to 120° C.; and baking both of said transparent conductive coating and said conductive reflective coating at a temperature of 130 to 400° C. in a state where said conductive reflective coating is directly on said transparent conductive coating. 